Mechanical grinding catalytic oxidation stirring device, manufacturing method thereof and application of mechanical grinding catalytic oxidation stirring device in wastewater treatment

Abstract

The invention discloses a mechanical grinding catalytic oxidation stirring device, a manufacturing method thereof and application of the mechanical grinding catalytic oxidation stirring device in wastewater treatment and belongs to the technical field of wastewater treatment. The mechanical grinding catalytic oxidation stirring device comprises a driving friction catalytic medicine permeating paddle, a driven friction stirring paddle and a support barrel, a friction groove in the inner wall of the driven friction stirring paddle is in friction fit with a first friction catalyst on the outer wall of the driving friction catalytic medicine permeating paddle, and the friction groove is in friction fit with a second friction catalyst on the outer wall of the driving friction catalytic medicine permeating paddle by adjusting rotation resistance and a friction gap. The rotation differential speed is adjusted, a catalyst is directly loaded on a mechanical grinding catalytic oxidation stirring device, and high-efficiency degradation of refractory organic pollutants can be realized by combining technologies such as mechanical grinding, friction catalysis and stirring with advanced oxidation.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of wastewater treatment, and relates to a mechanical grinding catalytic oxidation stirring device, a manufacturing method thereof, and application of the device in treatment of wastewater and in treatment of high-concentration refractory organic wastewater. BACKGROUND

[0002] Refractory organic wastewater, especially high-salt high-concentration refractory organic wastewater, is a problem in the field of water treatment due to its high concentration, high toxicity, difficulty in decomposition, and poor biodegradability. Catalytic persulfate oxidation, catalytic ozone oxidation, catalytic permanganate oxidation, Fenton oxidation, and other catalytic advanced oxidation methods are the most commonly used methods for treating such wastewater. These methods can mineralize organic matter at normal temperature and pressure, or significantly improve the biodegradability of wastewater, and thus are favored under the background of "double carbon". However, in practice, for perfluoro / polyfluoroalkyl compounds and other refractory organic wastewater, or complex organic wastewater such as landfill leachate, the catalytic decomposition and mineralization capacity is insufficient, and there are problems such as high chemical consumption and secondary pollution. At the same time, catalytic advanced oxidation methods often result in a decrease in the performance of the catalyst or even poisoning of the catalyst due to the deposition of catalytic decomposition products and other reasons. Therefore, improving the catalytic oxidation capacity, reducing chemical consumption, avoiding secondary pollution, and solving the problem of performance degradation of the catalyst during use are the keys to the treatment of refractory organic wastewater by catalytic oxidation.

[0003] Mechanical grinding includes ball milling, attrition milling, stirring, grinding, extrusion, and shearing, etc. Ball milling is often used for catalytic decomposition of difficult-to-degrade solid waste (Chen Huichao, et al. Application research progress of mechanical chemical method in environmental pollution control field[J]. Chemical Industry Progress, 2021, 40(11): 6332-6346. Wen Dan, et al. Research and application of mechanical force chemistry in the field of environment: bibliometric analysis based on ball milling method[J]. Applied Chemistry, 2025, 54(2): 439-445). Rubbing technology has been used in papermaking, solid waste treatment, feed processing, building material crushing, mineral processing, material preparation, traditional Chinese medicine component extraction, and many other fields; such as a rubbing machine disclosed in the papermaking application field, application number 201621266492X; a production process for preparing fibers by breaking the walls of plant raw materials, application number 2021102492532; a method for preparing pure pulp from sugarcane bagasse, application number 2015105962002; an ultrasonic office waste paper pulping process, application number 2020112140836; a preparation method of high-strength biochemi-pulp, application number 2021109143763; a wet-strength wiping paper loss paper recycling pulping method, application number 2022105145571; a refined bamboo pulp, a preparation method thereof, and application of the refined bamboo pulp in papermaking, application number 2022108055774, etc.; a cathode ray tube resource treatment method disclosed in the solid waste treatment application field, application number 031093035; a running method of a tire bead rubbing mechanism of a waste heavy-duty tire outer tire crushing robot, application number 2020101101255; a wheat pulverizer disclosed in the feed processing application field, application number 2011100710168; a rubbing shaping device for a vertical shaft impact crusher, disclosed in the building material crushing application field, application number 2013103075081; a flake graphite regrinder, disclosed in the mineral processing application field, application number 2016105646067; a lithium ion battery positive electrode material grinding device and its production process, disclosed in the material preparation application field, application number 2023107478579; a traditional Chinese medicine extraction method based on physical rubbing, disclosed in the traditional Chinese medicine component extraction application field, application number 2021108323913, etc.

[0004] Combining stirring and grinding has been disclosed in the field of material pulverization, such as a stirring mill for producing a suspension type ceramic insulator and a processing method, application number 2024108410084; an impact type stirring mill and a powder grinding system, application number 2024101927348; a stirring mill, application number 2023116611485; a grinding disc and a stirring mill having the same, application number 2023116611451; a stirring mill with multi-dimensional stirring, application number 2023111877726; a vertical rotary self-classifying stirring mill, application number 2023110735408; a stirring cylinder with a groove and a stirring mill, application number 2021110982533; a stirring mill and a method of operating and cleaning the stirring mill, application number 2020800617452; a multi-shaft stirring mill, application number 2017106494723; a spiral stirring mill for sepiolite, application number 2019111907621; a three-screw planetary transmission vertical medium stirring mill, application number 2015101960173, etc., but these technologies are all targeted at pulverizing materials, and if used for catalytic wastewater degradation of powder catalysts, the grinding intensity is large, the particle size of the catalyst will become smaller and smaller, and it is difficult to recover, resulting in loss, which cannot be applied in practice.

[0005] Friction catalysis is a catalytic technology developed in recent years (Lingbo Xiao, et al, Recent progress and prospect of friction-driven-tribocatalysis: From basic principle to material design, Surfaces and Interfaces 56 (2025) 105557; Xin Wang, et al Contrasting piezocatalytic and tribocatalytic behavior of BaTiO3, Materials Science in Semiconductor Processing 172 (2024) 108080; Xu Ying, Bi 12 TiO 20 Research on friction catalysis performance and mechanism, Zhejiang University of Technology Master's Thesis; Liu Siyu, Ba 1-x Sr x Preparation and Tribocatalytic Performance of BaTiO3 (x=0-0.3) Nanoparticles, Qilu University of Technology Master's Thesis; Gu Yanhong, et al, 2025100911671 Application of Alumina Substrate in Friction Catalytic Degradation of High Concentration Organic Dye Wastewater), but this technology has weak ability to catalytically degrade pollutants and cannot be used for degradation of refractory organic pollutants.

[0006] In the mechanical grinding or friction catalysis process, the catalyst can be structurally damaged or deactivated due to mechanical force, and the deposition of catalytic decomposition products on the catalyst surface can also cause the catalyst performance to decrease. The contact of pollutants with the catalyst and oxidant is the main factor determining the catalytic oxidation ability. By increasing the binding ability of pollutants to the catalyst through frictional charge transfer, moderate mechanical grinding can promote the combination of pollutants with the catalyst and oxidant and the renewal of the catalyst surface without damaging the catalyst. A high-efficiency and long-life catalytic oxidation device is the key to solving the environmental protection and low-carbon treatment of refractory organic wastewater.

[0007] Therefore, by combining mechanical grinding, friction catalysis, stirring and other technologies with advanced oxidation, a method and equipment with non-destructive mechanical grinding, friction catalysis and catalytic oxidation coupling can be designed and developed to achieve efficient degradation of refractory organic pollutants. SUMMARY

[0008] To solve the above problems, the present application provides a mechanical grinding catalytic oxidation stirring device and its manufacturing method and application in treating wastewater. The friction groove on the inner wall of the driven friction stirring paddle of the mechanical grinding catalytic oxidation stirring device is matched with the friction catalysis groove on the outer wall of the driven friction catalysis permeation paddle, and the rotational resistance and friction gap are adjusted to adjust the rotational differential speed. The catalyst is directly loaded on the mechanical grinding catalytic oxidation stirring device, and by combining mechanical grinding, friction catalysis, stirring and other technologies with advanced oxidation, efficient degradation of refractory organic pollutants can be achieved.

[0009] The mechanical grinding catalytic oxidation stirring device comprises a driving friction catalytic permeation paddle, a driven friction stirring paddle and a support barrel; the driving friction catalytic permeation paddle is a hollow cone, the outer wall of the cone is provided with friction catalytic arms, and the friction catalytic arms are arranged in multiple columns in a spiral upward manner, the gaps between the columns form spiral upward flow guide grooves, the spiral upward rotation direction of the flow guide grooves is opposite to the rotation direction of the driving friction catalytic permeation paddle, and the flow guide grooves and the hollow cavity are communicated through a permeation pipe; the driving friction catalytic permeation paddle is provided with the driven friction stirring paddle outside the cone; the bottom of the driven friction stirring paddle is an open lower end, the inner wall of the driven friction stirring paddle is matched with the friction catalytic arms on the outer wall of the driving friction catalytic permeation paddle in a friction mode, the inner wall of the driven friction stirring paddle is provided with spiral upward friction grooves, and the spiral rotation directions of the friction grooves and the flow guide grooves on the outer wall of the driving friction catalytic permeation paddle are opposite; the outer wall of the lower part of the driven friction stirring paddle is provided with stirring paddle blades, and the upper part of the driven friction stirring paddle is provided with liquid discharge holes penetrating the barrel wall above the friction grooves; the driving friction catalytic permeation paddle and the driven friction stirring paddle matched therewith are arranged on the support barrel, the friction gap between the driving friction catalytic permeation paddle and the driven friction stirring paddle is adjusted through the support arranged on the support barrel, the friction is changed, the rotation resistance adjuster on the driven friction stirring paddle is matched for adjustment, and the rotation differential speed adjustment of the driving friction catalytic permeation paddle and the driven friction stirring paddle is realized.

[0010] Further, the friction catalytic arms are formed by splicing multiple columns of friction catalytic arm pieces in a spiral manner and are externally hung on the surface of the cone; the gaps between the two columns of friction catalytic arm pieces form spiral upward flow guide grooves in the central axis direction of the cone; the hollow cavity of the cone is a liquid medicine cabin, the top of the liquid medicine cabin is provided with a liquid medicine tank, the liquid medicine cabin and the liquid medicine tank are connected, the liquid medicine tank is a closed cabin, a pressure adjuster is arranged on the cabin, a plug liquid medicine cabin cleaning port is arranged at the bottom of the liquid medicine cabin, the liquid medicine cabin and the flow guide grooves are communicated through multiple small permeation pipes, and the upper part of the driving friction catalytic permeation paddle is provided with an inner paddle suspension beam and a driven gear disc.

[0011] Further, the driven friction stirring paddle is an open cone barrel, the inner wall of the cone barrel is provided with spiral upward friction grooves, the starting point of the friction grooves is located at the open lower end of the cone barrel, the terminal point of the friction grooves is located at the upper part of the barrel wall, the upward rotation direction of the friction grooves is consistent with the rotation direction of the driving friction catalytic permeation paddle, the barrel wall at the terminal point of the friction grooves is provided with liquid discharge holes penetrating the barrel wall, the outer wall of the lower part of the driven friction stirring paddle is provided with stirring paddle blades, and the upper part of the driven friction stirring paddle is provided with an outer paddle suspension beam.

[0012] Further, the support barrel comprises a barrel body, a stand column support arranged on the upper part of the barrel body, and a support penetrating through the upper beam and the lower beam. An upper suspension beam is arranged on the upper beam and is integrated with the upper beam. The active friction catalysis permeation plough is fixed on the upper beam through the inner plough suspension beam and can rotate freely along the shaft. The driven friction stirring plough is fixed on the lower beam through the outer plough suspension beam and can rotate freely along the shaft. A height adjuster is arranged between the support and the upper beam to adjust the height of the upper beam, so as to adjust the friction gap between the active friction catalysis permeation plough and the driven friction stirring plough. A valve liquid discharge pipe is arranged at the lowest part of the barrel body.

[0013] Preferably, the active friction catalysis permeation plough is arranged in the cylinder cavity of the driven friction stirring plough. The outer wall of the active friction catalysis permeation plough is matched with the inner wall of the cylinder cavity of the driven friction stirring plough. The friction catalysis height of the outer surface of the active friction catalysis permeation plough is aligned with the friction groove height of the inner wall of the cylinder cavity of the driven friction stirring plough.

[0014] Preferably, the active friction catalysis permeation plough is fixed on the upper beam and the lower suspension beam of the support barrel through the inner plough suspension bearing arranged below the inner plough suspension beam, the upper stable bearing and the lower stable bearing on the outer wall. The active friction catalysis permeation plough can rotate freely along the central shaft of the cone. A driving motor and a driving wheel are arranged on the upper beam or the upper suspension beam. The driving wheel is engaged with the driven gear disc to drive the active friction catalysis permeation plough to rotate.

[0015] Preferably, the driven friction stirring plough is fixed on the lower beam of the support barrel through the outer plough suspension bearing arranged below the outer plough suspension beam, the upper stable bearing and the lower stable bearing on the outer wall. The driven friction stirring plough can rotate freely along the central shaft of the cone. A rotation resistance adjuster is arranged on the outer plough suspension beam to adjust the rotation resistance of the driven friction stirring plough.

[0016] Preferably, the active friction catalysis permeation plough is driven to rotate by the driving motor through the driving wheel engaging with the driven gear disc. The driven friction stirring plough is driven to rotate by the friction force between the active friction catalysis permeation plough and the driven friction stirring plough. The distance between the active friction catalysis permeation plough and the driven friction stirring plough can be adjusted by the height adjuster to change the friction force. The rotation resistance of the driven friction stirring plough can be changed by adjusting the rotation resistance adjuster, so as to adjust the stirring speed of the driven friction stirring plough and the friction force of the friction catalysis.

[0017] The rotation speed difference between the active friction catalysis permeation plough and the driven friction stirring plough causes the fluid to rise along the gap between the active friction catalysis permeation plough and the driven friction stirring plough under the spiral driving of the guide groove on the outer wall of the active friction catalysis permeation plough and the friction groove on the inner wall of the driven friction stirring plough. The fluid is discharged from the driven friction stirring plough through the liquid discharge hole arranged in the upper part of the driven friction stirring plough, so as to realize the circulation of the treated wastewater.

[0018] The friction catalytic mold is made of a porous ceramic material loaded with iron and manganese carbon and a catalyst, and the porous ceramic is one or more of alumina ceramic, mullite ceramic, zirconia ceramic, and silicon nitride ceramic.

[0019] The driven friction stirring paddle is made of polytetrafluoroethylene material, and the inner surface can be loaded with a catalyst.

[0020] The catalyst is selected from one or two of barium titanate, strontium titanate, barium strontium titanate, and bismuth titanate.

[0021] The preparation method of the mechanical grinding catalytic oxidation stirring device of the application comprises the preparation of the following key components and the installation according to the structure of the mechanical grinding catalytic oxidation stirring device, and specifically comprises the following steps: A: Preparation method of the driven friction catalytic permeation paddle: (1) Take the porous ceramic with a porosity of 40-60% and a pore size range of 0.2-100 μm, and process the friction catalytic mold into a mold piece with a required shape, and then immerse the mold piece in a 5-15% sulfuric acid solution under a micro-boiling state for 30-60 min, wash with water until neutral, immerse in a 1-2% sodium hydroxide solution under a micro-boiling state for 30-60 min, and wash with water until nearly neutral, and then dry for use; (2) Preparation of polyvinyl alcohol iron and manganese mixed solution: take ferrous salt, ferric salt, and divalent manganese salt in a molar ratio of (0.5-1):1:1, dissolve in a 0.1-0.3 mol / L polyvinyl alcohol solution, and configure into an iron and manganese mixed solution with a total molar concentration of 1-2 mol / L and containing 0.1-0.2 mol / L polyvinyl alcohol; (3) Take catalyst powder with a particle size range of 10-100 nm, immerse in a 0.1-1 mol / L hydrogen peroxide solution, ultrasonic dispersion homogenization, heat at 80-100°C for 30-60 min, add potassium hydroxide to make the concentration of potassium hydroxide in the solution 1-3 mol / L, and obtain an alkaline catalyst suspension liquid containing 2-5 g / L of nano catalyst; (Four) the porous ceramic of step (one) is immersed in the iron manganese mixed solution of step (two), is placed in a vacuum container, is vacuumized to relative pressure ≤-0.09MPa, pressure is kept for 30-60min, restores normal pressure, takes out 45-65 DEG C and dries, again sprays the iron manganese mixed solution to the porous ceramic, until saturation is absorbed, dries again, adds again, saturation is absorbed, same temperature dries, repeats spraying saturation and dries, until no longer absorption, finally dries and is placed in a vacuum high-temperature furnace, vacuumizes to relative pressure ≤-0.09MPa, heats, is heated to 500-900 DEG C at a speed of 3~5 DEG C / min, keeps temperature for 2-4h, cools to room temperature in the furnace, and the porous ceramic of iron manganese carbon loading piece is obtained;The alkaline catalyst suspension obtained in step (three) is sprayed on the outer surface of the porous ceramic of iron manganese carbon loading piece until saturation is absorbed, and is immersed for 12-24h, and is placed in a vacuum high-temperature furnace again, is vacuumized to relative pressure for-0.09MPa, is heated to 600-800 DEG C at a speed of 3~5 DEG C / min, and is kept temperature for 1-2h, and is cooled to room temperature in the furnace, and is washed to neutral, and the friction catalyst A is obtained, and the porosity is not less than 30%, that is, qualified; (Five) the friction catalyst A of step (four) is installed on a hollow cone, and the A piece is arranged spirally upward, with a gap of 0.1-5mm between the columns, forming a spiral upward flow guide groove, and a through hole with a hole diameter of 0.01-0.2mm is opened on the wall of the hollow cone corresponding to the flow guide groove, and after installation, a driven friction stirring paddle is obtained; B: the method for loading catalyst on the inner surface of polytetrafluoroethylene when the driven friction stirring paddle is polytetrafluoroethylene (1) polytetrafluoroethylene material is taken, and is processed into the required shape and size, and the surface is polished and cleaned with No.100 sandpaper to obtain a polytetrafluoroethylene blank; (2) catalyst powder with a particle size range of 10-100nm is taken, is added into 0.1-1mol / L hydrogen peroxide solution, is uniformly dispersed by ultrasonic, the pH value is adjusted to 10-11 by sodium hydroxide solution, the hydrogen peroxide is decomposed by heating and boiling, and the excess water is volatilized, to obtain a catalyst suspension with a solid content of 40-60%; according to the mass ratio, the catalyst powder:PTFE is 1: (4-6), and the polytetrafluoroethylene (PTFE) emulsion with a solid content of 20-30% is mixed with the nano-catalyst suspension, and is uniformly dispersed by ultrasonic to obtain a catalyst mixed emulsion; (3) the catalyst mixed emulsion is uniformly coated on the inner wall surface of the polytetrafluoroethylene blank, is pre-dried at 80~100 DEG C for 1~2 hours to remove water, is heated to 120 DEG C and kept for 30 minutes, is continuously heated to 280~300 DEG C and kept for 10~20 minutes, and is slowly cooled to room temperature in the furnace, to obtain a driven friction stirring paddle with catalyst loaded on the surface.

[0022] The application of the mechanical grinding catalytic oxidation stirring device of the application to treat wastewater comprises the following application methods: The wastewater to be treated is placed in the barrel body of the support barrel, the pH value is adjusted, the height adjuster is adjusted so that the active friction catalytic permeation paddle and the driven friction stirring paddle have a suitable gap, the oxidant solution is injected into the medicine liquid tank and into the medicine liquid cabin, the driving motor is started, the driving wheel is engaged with the transmission, the driven gear plate is rotated, the active friction catalytic permeation paddle is rotated towards the upward direction of the spiral flow guide groove, the height adjuster is continuously adjusted so that the driven friction stirring paddle is in contact with the active friction catalytic permeation paddle, under the action of friction, the driven friction stirring paddle also rotates, and the stirring of the wastewater in the barrel is realized; the rotation resistance adjuster of the driven friction stirring paddle is adjusted so that the driven friction stirring paddle obtains a speed difference through the resistance and the friction force of the active friction catalytic permeation paddle, and the wastewater to be treated is lifted along the gap between the active friction catalytic permeation paddle and the driven friction stirring paddle under the driving of the friction grooves on the inner wall of the driven friction stirring paddle and the spiral upward flow guide groove on the surface of the active friction catalytic permeation paddle, and finally is discharged from the liquid discharge hole on the driven friction stirring paddle and flows back into the barrel, and the cycle is completed; in this process, the size of the pressure regulator switch is adjusted to change the pressure in the medicine liquid cabin, the oxidant penetrates into the friction catalytic chamber along the permeation pipe, reacts with the pollutants in the wastewater on the catalyst of the friction catalytic chamber, and at the same time, due to the existence of the speed difference between the active friction catalytic permeation paddle and the driven friction stirring paddle, the friction force of the outer surface friction catalytic chamber of the active friction catalytic permeation paddle and the inner surface friction force of the driven friction stirring paddle act on the catalyst, the wastewater and the oxidant, the organic matter in the wastewater is decomposed, the decomposition and mineralization of the harmful substances in the wastewater are realized, when the wastewater treatment reaches the standard, the valve of the liquid discharge pipe is opened, and the wastewater is discharged, and the wastewater treatment is completed.

[0023] The oxidant is one or several of hydrogen peroxide, potassium persulfate and potassium permanganate.

[0024] The mechanical grinding, friction catalysis, advanced catalytic oxidation and stirring technology of the application are integrated, and the mechanical grinding catalytic oxidation stirring device and the preparation and application thereof in treating wastewater have the following advantages. I. The mechanical chemical, friction catalysis, advanced oxidation and stirring are coupled, the advantages of multiple technologies are integrated, the decomposition of organic pollutants is strong, and the efficiency is high. II. The active friction catalytic permeation paddle and the driven friction stirring paddle are designed, the friction force is easy to control, the catalyst wear and loss are reduced, the deposition of degradation products on the catalyst surface is reduced, and the catalytic performance is high. III. The spiral flow guide groove, the medicine liquid cabin and the permeation pipe are combined and designed, the wastewater flows along the friction gap between the active friction catalytic permeation paddle and the driven friction stirring paddle, the medicine liquid is uniformly added, the organic matter to be treated in the wastewater, the oxidant and the catalyst are fully and uniformly contacted, the catalytic effect is good, the medicine consumption is greatly reduced, and the catalytic decomposition efficiency is improved. Four, through the friction force between the active friction catalytic permeation paddle and the driven friction stirring paddle and the resistance control of the driven friction stirring paddle, as well as the stirring paddle on the driven friction stirring paddle, the speed difference between the active friction catalytic permeation paddle and the driven friction stirring paddle and the stirring intensity of the wastewater in the barrel are realized, and the proportion of mechanical grinding, friction catalysis and advanced oxidation is realized, which is suitable for different types of wastewater, energy saving and medicine saving; Five, the friction catalysis design is easy to replace and maintain, and is high in efficiency and saving; Six, the preparation method of the friction catalysis adopts adsorption carbonization combination, high loading capacity, firm loading, synchronous realization of friction catalyst loading solidification, carbonization activation and manganese iron conversion, process simplification, and the prepared catalysis has stronger wear resistance, friction catalysis, adsorption and chemical oxidation catalytic capacity; Seven, the friction groove and the gap between the friction catalysis pieces form a guide groove, which drives the liquid flow together, realizes synchronous liquid flow of friction catalysis, and does not need pump and other drives, which is energy saving and efficient; the catalyst surface is continuously updated during the catalytic process, and the friction catalysis and chemical catalytic efficiency are higher; Eight, the device is simple, practical, easy to use, widely applicable, and has high economic and environmental benefits. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 It is a schematic diagram of a mechanical grinding catalytic oxidation stirring device; Figure 2 It is a schematic diagram of the internal structure of a mechanical grinding catalytic oxidation stirring device; Figure 3 It is a schematic diagram of the overall structure of the active friction catalytic permeation paddle; Figure 4 It is a schematic diagram of the internal structure of the active friction catalytic permeation paddle; Figure 5 It is a schematic diagram of the external structure of the driven friction stirring paddle; Figure 6 It is a schematic diagram of the internal structure of the driven friction stirring paddle; Figure 7 It is a water sample treatment result; In the above figure: 1 is the main friction catalytic permeation paddle, 2 is the driven friction stirring paddle, 3 is the bracket barrel, 11 is the friction catalytic shell, 111 is the guide groove, 12 is the liquid tank, 121 is the liquid tank, 1211 is the pressure regulator, 122 is the liquid tank with a cleaning port, 13 is the permeation pipe, 14 is the inner paddle suspension beam, 15 is the driven gear disc, 20 is the friction groove, 21 is the stirring paddle, 22 is the liquid discharge hole, 23 is the outer paddle suspension beam, 31 is the barrel body, 32 is the vertical column support, 33 is the upper beam, 34 is the upper suspension beam, 35 is the lower beam, 321 is the height adjuster, 331 is the inner paddle suspension bearing, 332 is the upper stable bearing of the inner paddle, 333 is the lower stable bearing of the inner paddle, 334 is the driving motor, 335 is the driving wheel, 351 is the outer paddle suspension bearing, 352 is the upper stable bearing of the outer paddle, 353 is the lower stable bearing of the outer paddle, and 354 is the rotation resistance adjuster. DETAILED DESCRIPTION

[0026] The application will be further described in detail below with reference to the examples.

[0027] Example 1 This example is a mechanical grinding catalytic oxidation stirring device 1 and its preparation method: The mechanical grinding catalytic oxidation stirring device, the structure diagram is shown in Figure 1 and Figure 2 , including the main friction catalytic permeation paddle 1, the driven friction stirring paddle 2 and the bracket barrel 3; the main friction catalytic permeation paddle 1 is a hollow cone, the structure diagram is shown in Figure 3 and Figure 4 , the outer wall of the cone is provided with the friction catalytic shell 11 and the spiral upward guide groove 111, the spiral upward guide groove rotates in the opposite direction of the rotation direction of the main friction catalytic permeation paddle 1, the guide groove 111 and the hollow cavity are communicated through the permeation pipe 13; the driven friction stirring paddle 2 is sleeved outside the cone of the main friction catalytic permeation paddle 1; the bottom of the driven friction stirring paddle 2 is an open lower end, the structure diagram is shown in Figure 5 and Figure 6The inner wall of the driven friction stirring paddle 2 is matched with the friction catalysis of the outer wall of the driving friction catalysis permeation paddle 1, the inner wall of the driven friction stirring paddle 2 is provided with a spiral ascending friction groove 20, the spiral rotating direction of the friction groove 20 and the guide groove 111 of the outer wall of the driving friction catalysis permeation paddle 1 is opposite, the outer wall of the lower part of the cone barrel of the driven friction stirring paddle 2 is provided with a stirring paddle blade 21, and the liquid discharge hole 22 penetrating the barrel wall is arranged above the friction groove 20; the driving friction catalysis permeation paddle 1 and the driven friction stirring paddle 2 matched therewith are arranged on the support barrel 3, and the friction gap between the driving friction catalysis permeation paddle 1 and the driven friction stirring paddle 2 is adjusted through the support arranged on the support barrel 3, so as to change the friction force, and the rotation resistance adjuster 354 on the driven friction stirring paddle 2 is matched to adjust, so as to realize the rotation differential adjustment of the driving friction catalysis permeation paddle 1 and the driven friction stirring paddle 2.

[0028] The cone surface of the cone body of the driving friction catalysis permeation paddle 1 is provided with a porous ceramic friction catalysis 11 made of porous ceramic (one of alumina ceramic, mullite ceramic, zirconia ceramic and silicon nitride ceramic) loaded with iron-manganese-carbon and catalyst (one or more of barium titanate, strontium titanate, barium strontium titanate or bismuth titanate), the friction catalysis 11 is a plurality of spliced spiral plates arranged outside the surface of the cone body, in the central axis direction of the cone body, the gap between the two rows of plates forms a spiral ascending guide groove 111, the rotating direction of the guide groove 111 is opposite to the rotating direction of the driving friction catalysis permeation paddle 1; the hollow cavity of the cone body is a liquid medicine cabin 12, the top of the liquid medicine cabin 12 is provided with a liquid medicine groove 121, the liquid medicine cabin 12 and the liquid medicine groove 121 are connected, the liquid medicine groove is a closed cabin, and a pressure regulator 1211 is arranged on the top, the bottom of the liquid medicine cabin 12 is provided with a liquid medicine cabin cleaning port 122 with a plug, the liquid medicine cabin 12 and the guide groove 111 are communicated through a plurality of small permeation pipes 13, and the upper part of the driving friction catalysis permeation paddle 1 is provided with an inner paddle suspension beam 14 and a driven gear disc 15.

[0029] The driven friction stirring paddle 2 is an upper and lower open polytetrafluoroethylene cone barrel, the inner surface of the cone barrel is loaded with catalyst (one or more of barium titanate, strontium titanate, barium strontium titanate or bismuth titanate), and the inner wall is provided with a spiral ascending friction groove 20, the starting point of the friction groove 20 is located at the lower open mouth of the cone barrel, the terminal point is located at the upper part of the barrel wall, and the ascending rotating direction is consistent with the rotating direction of the driving friction catalysis permeation paddle 1, the barrel wall at the terminal point of the friction groove is provided with a liquid discharge hole 22 penetrating the barrel wall, the outer wall of the lower part of the cone barrel of the driven friction stirring paddle 2 is provided with a stirring paddle blade 21, and the upper part is provided with an outer paddle suspension beam 23.

[0030] The support barrel 3 is made of stainless steel, including a barrel body 31, a stand 32 arranged on the upper part of the barrel body, the stand 32 penetrating through an upper beam 33 and a lower beam 35, an upper suspension beam 34 being arranged on the upper beam and being integral with the upper beam, the active friction catalytic permeation paddle 1 being fixed on the upper beam through an inner paddle suspension beam 14 and being freely rotatable along the shaft, the driven friction stirring paddle 2 being fixed on the lower beam through an outer paddle suspension beam 23 and being freely rotatable along the shaft, an adjuster 321 being arranged between the stand 32 and the upper beam 33 to adjust the height of the upper beam 33, so as to adjust the friction gap between the active friction catalytic permeation paddle 1 and the driven friction stirring paddle 2, and a valve drain pipe 311 being arranged at the lowest part of the barrel body 31.

[0031] The active friction catalytic permeation paddle 1 is arranged in the cylinder cavity of the driven friction stirring paddle 2, the outer wall of the active friction catalytic permeation paddle 1 is matched with the inner wall of the cylinder cavity of the driven friction stirring paddle 2, and the height of the friction catalytic layer 11 on the outer surface of the active friction catalytic permeation paddle 1 is aligned with the height of the friction groove 20 on the inner wall of the cylinder cavity of the driven friction stirring paddle 2.

[0032] The active friction catalytic permeation paddle 1 is fixed on the upper beam 33 and the lower suspension beam 34 of the support barrel 3 through the inner paddle suspension bearing 331 arranged below the inner paddle suspension beam 14, the inner paddle upper stable bearing 332 and the inner paddle lower stable bearing 333 on the outer wall, so as to realize the free rotation of the active friction catalytic permeation paddle 1 along the central shaft of the cone, a driving motor 334 and a driving wheel 335 being arranged on the upper beam 33 or the upper suspension beam 34, the driving wheel 335 being engaged with the driven gear disc 15 to realize the rotation of the active friction catalytic permeation paddle 1.

[0033] The driven friction stirring paddle 2 is fixed on the lower beam 35 of the support barrel 3 through the outer paddle suspension bearing 351 arranged below the outer paddle suspension beam 23, the outer paddle upper stable bearing 352 and the outer paddle lower stable bearing 353 on the outer wall, so as to realize the free rotation of the driven friction stirring paddle 2 along the central shaft of the cone, and a rotation resistance adjuster 354 being arranged on the outer paddle suspension beam 23 to adjust the rotation resistance of the driven friction stirring paddle 2.

[0034] The active friction catalytic permeation paddle 1 is driven to rotate by the driving motor 334 through the driving wheel 335 engaging the driven gear disc 15, the rotation of the driven friction stirring paddle 2 is realized by the friction force between the active friction catalytic permeation paddle 1 and the driven friction stirring paddle 2, the distance between the active friction catalytic permeation paddle 1 and the driven friction stirring paddle 2 can be adjusted by the height adjuster 321 to change the friction force, the rotation resistance of the driven friction stirring paddle 2 is changed by adjusting the rotation resistance adjuster 354, and then the stirring speed of the driven friction stirring paddle 2 and the friction force of the friction catalysis are adjusted.

[0035] The rotation speed difference between the active friction catalytic permeation paddle 1 and the driven friction stirring paddle 2 causes the fluid to rise along the gap between the active friction catalytic permeation paddle 1 and the driven friction stirring paddle 2 under the spiral driving of the guide groove 111 on the outer wall of the active friction catalytic permeation paddle 1 and the friction groove 20 on the inner wall of the driven friction stirring paddle 2, and the fluid is discharged from the driven friction stirring paddle 2 through the liquid discharge hole 22 arranged in the upper part of the driven friction stirring paddle 2, so as to realize the circulation of the treated wastewater.

[0036] A preparation method of the mechanical grinding catalytic oxidation stirring device, including the preparation of the following key components and the installation according to the structure of the mechanical grinding catalytic oxidation stirring device, wherein the active friction catalytic permeation paddle: the friction catalytic A is the alumina porous ceramic loaded with iron manganese carbon and barium titanate; the driven friction stirring paddle is polytetrafluoroethylene loaded with barium titanate, and the preparation condition parameters specifically include the following steps. A: the preparation method of the active friction catalytic permeation paddle: (1) take the alumina porous ceramic with a porosity of 50% and a pore size range of 1-100 μm, which meets the technical requirements of the national standard "GB / T 16533-1996, General Technical Conditions for Porous Ceramic Products", process the friction catalytic A into the required shape of the A piece, immerse it in a 10% sulfuric acid solution under a micro-boiling state for 50 min, wash it with water until it is neutral, then immerse it in a 2% sodium hydroxide solution under a micro-boiling state for 50 min, wash it with water until it is nearly neutral, and dry it for use; (2) polyvinyl alcohol iron manganese mixed solution preparation: take ferrous salt, ferric salt and divalent manganese salt in a molar ratio of 1:1:1, dissolve them in a 0.2 mol / L polyvinyl alcohol solution, and configure them into an iron manganese mixed solution with a total molar concentration of 1 mol / L containing 0.2 mol / L polyvinyl alcohol; (3) take the barium titanate catalyst powder with a particle size range of 10-100 nanometers, immerse it in a 1 mol / L hydrogen peroxide solution, ultrasonic dispersion homogenization, heat it to 90°C for 45 min, add potassium hydroxide to make the concentration of potassium hydroxide in the solution 1 mol / L, and obtain an alkaline catalyst suspension containing 5 g / L of nano catalyst; (Four) the porous ceramic of step one is immersed in the iron-manganese mixed solution of step two, placed in a vacuum container, vacuumed to a relative pressure of ≤-0.09 MPa, pressure-kept for 60 min, the normal pressure is restored, taken out and dried at 50°C, the iron-manganese mixed solution is sprayed on the porous ceramic until saturated absorption, dried again, added dropwise again, saturated absorption, dried again at the same temperature, repeated spraying, saturated absorption and drying until no longer absorbed, finally dried and placed in a vacuum high-temperature furnace, vacuumed to a relative pressure of ≤-0.09 MPa, heated, and heated to 500°C at a rate of 3°C / min, kept for 3 h, cooled to room temperature in the furnace, to obtain the iron-manganese carbon loaded alumina porous ceramic sheet A; the alkaline barium titanate catalyst suspension obtained in step three is sprayed on the outer surface of the iron-manganese carbon loaded porous ceramic sheet A until saturated absorption, immersed for 24 h, placed in a vacuum high-temperature furnace again, vacuumed to a relative pressure of-0.09 MPa, heated to 600°C at a rate of 3°C / min, kept for 2 h, cooled to room temperature in the furnace, washed with water to neutral, to obtain the barium titanate alumina porous ceramic friction catalyst A, the porosity is detected to be 41%, not less than 30%, which is qualified; (Five) the friction catalyst A of step (four) is installed on a hollow cone, the A sheets are arranged in a spiral upward, with a gap of 0.5 mm between the columns to form a spiral upward flow guide groove, and a through hole with a hole diameter of 0.01 mm is opened on the wall of the hollow cone corresponding to the flow guide groove, after installation, a driven friction stirring paddle 1 is obtained; B: Method for loading catalyst on the inner surface of polytetrafluoroethylene when the driven friction stirring paddle is polytetrafluoroethylene (1) Take polytetrafluoroethylene material, process it into the required shape and size, polish and clean the surface with No. 100 sandpaper, to obtain a polytetrafluoroethylene blank; (2) Take barium titanate catalyst powder with a particle size range of 10-100 nanometers, directly add it into a 0.5 mol / L hydrogen peroxide solution, ultrasonic dispersion, adjust the pH value to 11 with sodium hydroxide solution, heat and boil to decompose hydrogen peroxide, and volatilize excess water, to obtain a catalyst suspension with a solid content of 50%; according to the mass ratio of catalyst powder: PTFE of 1:5, mix another polytetrafluoroethylene (PTFE) emulsion with a solid content of 20% with the nano-catalyst suspension, ultrasonic dispersion, to obtain a catalyst mixed emulsion; (3) evenly coat the catalyst mixed emulsion on the inner wall surface of the polytetrafluoroethylene blank, pre-dry at 90°C for 2 hours to remove water, heat to 120°C for 30 minutes, continue to heat to 300°C for 10 minutes, slowly cool to room temperature in the furnace, to obtain a driven friction stirring paddle 1 with catalyst loaded on the surface.

[0037] Example 2 This example is a mechanical grinding catalytic oxidation stirring device 2 and a preparation method thereof: The mechanical grinding catalytic oxidation stirring device 2 is composed of the same structure as in Example 1, and the preparation method thereof comprises the preparation of the following key components and the installation according to the structure of the mechanical grinding catalytic oxidation stirring device as described, wherein the driving friction catalytic permeation paddle 2: the friction catalytic A is an alumina porous ceramic loaded with iron manganese carbon and strontium titanate + barium titanate; the driven friction stirring paddle 2 is polytetrafluoroethylene loaded with strontium titanate and barium titanate, and the preparation condition parameters are as follows: A: Preparation method of the driving friction catalytic permeation paddle: (1) Take the alumina porous ceramic with a porosity of 60% and a pore size range of 1-100 μm, which meets the technical requirements of the national standard “GB / T 16533-1996, General Technical Conditions for Porous Ceramic Products”, process the friction catalytic A into the required shape of the paddle, soak it in a 5% sulfuric acid solution under a micro-boiling state for 40 min, wash it with water until it is neutral, then soak it in a 1% sodium hydroxide solution under a micro-boiling state for 60 min, wash it with water until it is nearly neutral, and dry it for use; (2) Preparation of polyvinyl alcohol iron manganese mixed solution: take ferrous salt, iron salt and divalent manganese salt in a molar ratio of 0.5:1:1, dissolve them in a 0.3 mol / L polyvinyl alcohol solution, and configure them into an iron manganese mixed solution with a total molar concentration of 2 mol / L containing 0.1 mol / L polyvinyl alcohol; (3) Take the strontium titanate and barium titanate (strontium titanate and barium titanate in a mass ratio of 1:1) catalyst powder with a particle size range of 10-100 nanometers, immerse it in a 1 mol / L hydrogen peroxide solution, ultrasonic dispersion homogenization, heat to 100°C for 30 min, add potassium hydroxide to make the potassium hydroxide concentration in the solution 3 mol / L, and obtain an alkaline mixed catalyst suspension containing 5 g / L of nano catalyst; (Four) the porous ceramic of step one is immersed in the iron-manganese mixed solution of step two, placed in a vacuum container, vacuumed to a relative pressure of ≤-0.09 MPa, pressure-kept for 60 min, the normal pressure is restored, taken out and dried at 45℃, the iron-manganese mixed solution is sprayed on the porous ceramic until saturated absorption, dried again, added dropwise again, saturated absorption, dried again at the same temperature, repeated spraying, saturated absorption and drying until no longer absorbed, finally dried and placed in a vacuum high-temperature furnace, vacuumed to a relative pressure of ≤-0.09 MPa, heated, and heated to 900℃ at a rate of 5℃ / min, kept for 2h, cooled in the furnace to room temperature, to obtain the iron-manganese carbon loaded alumina porous ceramic sheet A; the alkaline strontium titanate-barium titanate mixed catalyst suspension obtained in step three is sprayed on the outer surface of the iron-manganese carbon loaded porous ceramic sheet A until saturated absorption, immersed for 20h, placed in a vacuum high-temperature furnace again, vacuumed to a relative pressure of-0.09 MPa, heated to 800℃ at a rate of 5℃ / min, activated for 1h, cooled to room temperature in the furnace, washed with water to neutral, to obtain the iron-manganese carbon and strontium titanate-barium titanate loaded alumina porous ceramic friction catalyst A, the porosity is 35% (not less than 30%), which is qualified; (Five) the friction catalyst A of step four is installed on a hollow cone, the A sheets are arranged in a spiral upward, with a gap of 5mm between the columns to form a spiral upward flow guide groove, a through hole with a hole diameter of 0.2mm is opened on the wall of the hollow cone corresponding to the flow guide groove, after installation, the active friction catalyst drug infiltration paddle 2 is obtained; B: method for loading catalyst on the inner surface of polytetrafluoroethylene when the driven friction stirring paddle is polytetrafluoroethylene (1) polytetrafluoroethylene material is taken, processed into the required shape and size, and the surface is polished and cleaned with No. 100 sandpaper to obtain a polytetrafluoroethylene blank; (2) strontium titanate and barium titanate (mass ratio of strontium titanate to barium titanate is 1:1) catalyst powder with a particle size range of 10-100 nanometers is taken, directly added into 1 mol / L hydrogen peroxide solution, ultrasonically dispersed uniformly, the pH value is adjusted to 11 with sodium hydroxide solution, heated and boiled to decompose hydrogen peroxide, and the excess water is volatilized to obtain a catalyst suspension with a solid content of 60%; according to the mass ratio of catalyst powder: PTFE of 1:4, another polytetrafluoroethylene (PTFE) emulsion with a solid content of 30% is mixed with the nano-catalyst suspension, ultrasonically dispersed uniformly to obtain a catalyst mixed emulsion; (3) the catalyst mixed emulsion is uniformly coated on the inner wall surface of the polytetrafluoroethylene blank, pre-dried at 100℃ for 2 hours to remove water, heated to 120℃ for 30 minutes, continuously heated to 300℃ for 15 minutes, and slowly cooled to room temperature in the furnace to obtain a driven friction stirring paddle 2 with a surface loaded catalyst.

[0038] Example 3 This example is a mechanical grinding catalytic oxidation stirring device 3 and its preparation method: The mechanical grinding catalytic oxidation stirring device 3 has the same structure as that of the embodiment 1, and the preparation method thereof comprises the following steps of preparing key components and installing the mechanical grinding catalytic oxidation stirring device according to the structure as described, wherein the driving friction catalytic permeation paddle 3 is a friction catalytic A made of an alumina porous ceramic loaded with iron manganese carbon and barium titanate, and the driven friction stirring paddle 3 is a polytetrafluoroethylene loaded with barium titanate, and the preparation condition parameters are as follows: A: Preparation method of the driving friction catalytic permeation paddle: (1) The alumina porous ceramic with a porosity of 60% and a pore size range of 1-100 μm is processed into the A piece of the friction catalytic A in a required shape, and then soaked in a 15% sulfuric acid solution under a micro-boiling state for 60 min, washed with water until neutral, soaked in a 2% sodium hydroxide solution under a micro-boiling state for 30 min, washed with water until nearly neutral, and dried for use; (2) Preparation of the polyvinyl alcohol iron manganese mixed solution: ferrous salt, ferric salt and divalent manganese salt are taken in a molar ratio of 1:1:1, dissolved in a 0.1 mol / L polyvinyl alcohol solution, and configured into an iron manganese mixed solution with a total molar concentration of 1 mol / L containing 0.1 mol / L polyvinyl alcohol; (3) The barium titanate catalyst powder with a particle size range of 10-100 nanometers is immersed in a 0.1 mol / L hydrogen peroxide solution, ultrasonically dispersed and homogenized, activated at 80°C for 60 min, and then potassium hydroxide is added to make the concentration of potassium hydroxide in the solution 1 mol / L, so as to obtain an alkaline catalyst suspension liquid containing 2 g / L of nano catalyst; (4) The porous ceramic in step 1 is immersed in the iron manganese mixed solution in step 2, placed in a vacuum container, vacuumized to a relative pressure ≤-0.09 MPa, pressure-kept for 30 min, restored to normal pressure, taken out and dried at 65°C, and then the iron manganese mixed solution is sprayed onto the porous ceramic until saturated absorption, dried, and then repeated the spraying, saturated absorption and drying until no more absorption, and finally dried and placed in a vacuum high-temperature furnace, vacuumized to a relative pressure ≤-0.09 MPa, heated, and then heated to 500°C at a speed of 3°C / min, kept for 4 h, cooled to room temperature in the furnace, and thus the alumina porous ceramic A loaded with iron manganese carbon is obtained; the alkaline barium titanate catalyst suspension liquid obtained in step 3 is sprayed onto the outer surface of the alumina porous ceramic A loaded with iron manganese carbon until saturated absorption, immersed for 12 h, and then placed in a vacuum high-temperature furnace again, vacuumized to a relative pressure of -0.09 MPa, heated to 600°C at a speed of 3°C / min, kept for 2 h, cooled to room temperature in the furnace, washed with water until neutral, and thus the friction catalytic A of the alumina porous ceramic loaded with iron manganese carbon and barium titanate is obtained, and the porosity is detected to be 32%, which is not less than 30%, and thus qualified. (V) install the step four friction catalytic A on the hollow cone, the A sheet is arranged spirally upward, the gap of 0.5mm is left between the columns, the spiral upward flow guide groove is formed, the through hole with the hole diameter of 0.1mm is opened on the hollow cone wall corresponding to the flow guide groove, after the installation is completed, the active friction catalytic permeation paddle is obtained; B: the method for loading catalyst on the inner surface of the driven friction stirring paddle when the driven friction stirring paddle is polytetrafluoroethylene (1) take the polytetrafluoroethylene material, process into the required shape and size, polish the clean surface with No. 100 sandpaper, and obtain the polytetrafluoroethylene blank; (2) take the barium titanate catalyst powder with the particle size range of 10-100 nanometers, directly put into the 0.1 mol / L hydrogen peroxide solution, ultrasonic dispersion is uniform, adjust the pH value to 10 with sodium hydroxide solution, heat and boil to decompose hydrogen peroxide, and volatilize the excess water to obtain the catalyst suspension with the solid content of 40%; according to the mass ratio of catalyst powder: PTFE is 1: 6), another polytetrafluoroethylene (PTFE) emulsion with the solid content of 20% is mixed with the nano catalyst suspension, ultrasonic dispersion is uniform, and the catalyst mixed emulsion is obtained; (3) evenly coat the catalyst mixed emulsion on the inner wall surface of the polytetrafluoroethylene blank, pre-dry at 80°C for 1 hour to remove water, heat to 120°C for 30 minutes, continue to heat to 280°C for 20 minutes, slowly cool to room temperature in the furnace, and obtain the driven friction stirring paddle 3 with the surface loaded catalyst.

[0039] Example 4 The embodiment is a mechanical grinding catalytic oxidation stirring device 4 and a preparation method thereof: The structure of the mechanical grinding catalytic oxidation stirring device 4 is the same as that of example 1, and the preparation method thereof comprises the preparation of the following key components and the installation according to the structure of the mechanical grinding catalytic oxidation stirring device, wherein the active friction catalytic permeation paddle 4: the friction catalytic A is an alumina porous ceramic loaded with iron manganese carbon and barium titanate; the driven friction stirring paddle 4 is polytetrafluoroethylene loaded with barium titanate, and the preparation condition parameters are as follows: A: the preparation method of the active friction catalytic permeation paddle: (I) take the alumina porous ceramic with the porosity of 50% and the pore size range of 1-100 μm, and the technical requirements meet the provisions of the national standard "GB / T 16533-1996, General Technical Conditions for Porous Ceramic Products", process the friction catalytic A sheet with the required shape, soak in the 12% sulfuric acid solution under the micro-boiling state for 40 min, wash to neutral, then soak in the 2% sodium hydroxide solution under the micro-boiling state for 50 min, wash to near neutral, and dry for use; (ii) Preparation of polyvinyl alcohol iron manganese mixed solution: take ferrous salt, ferric salt and divalent manganese salt in a molar ratio of 0.5:1:1, dissolve in a 0.1 mol / L polyvinyl alcohol solution, and configure into an iron manganese mixed solution containing 0.1 mol / L polyvinyl alcohol with a total molar concentration of 1 mol / L; (iii) Take barium titanate catalyst powder with a particle size range of 10-100 nanometers, immerse it in a 0.5 mol / L hydrogen peroxide solution, ultrasonic dispersion homogenization, heat to 90°C for 40 minutes, add potassium hydroxide to make the concentration of potassium hydroxide in the solution 2 mol / L, and obtain a basic catalyst suspension containing 4 g / L of nano catalyst; (iv) Immerse the porous ceramic of step one in the iron manganese mixed solution of step two, place it in a vacuum container, and vacuum to a relative pressure ≤-0.09 MPa, keep the pressure for 50 minutes, restore the normal pressure, take out and dry at 50°C, then spray the iron manganese mixed solution onto the porous ceramic until it is saturated, and then dry again. Repeat the spraying, absorbing, and drying until no more absorption is observed. Finally, dry and place in a vacuum high-temperature furnace, vacuum to a relative pressure ≤-0.09 MPa, heat to 800°C at a rate of 4°C / min, and keep the temperature for 3 hours. Cool the furnace to room temperature to obtain the iron manganese carbon loaded alumina porous ceramic sheet A. Spray the basic barium titanate catalyst suspension obtained in step three onto the outer surface of the iron manganese carbon loaded porous ceramic sheet A until it is saturated, immerse for 18 hours, and then place it in a vacuum high-temperature furnace again. Vacuum to a relative pressure of -0.09 MPa, heat to 800°C at a rate of 4°C / min, and keep the temperature for 1 hour. Cool the furnace to room temperature, wash with water until neutral, and obtain the iron manganese carbon and barium titanate loaded alumina porous ceramic friction catalyst A4. The porosity is 38%, not less than 30%, which is qualified; (v) Install the friction catalyst A of step four on a hollow cone, arrange the sheet in a spiral upward with a gap of 4 mm between the columns to form a spiral upward flow channel. The corresponding hollow cone wall has a 0.1 mm diameter through hole. After installation, the active friction catalyst drug infiltration paddle is obtained. B: Method for loading catalyst on the inner surface of polytetrafluoroethylene driven friction stirring paddle (1) Take polytetrafluoroethylene material, process it into the required shape and size, and polish the clean surface with 100 grit sandpaper to obtain polytetrafluoroethylene blank; (2) Take the titanium barium catalyst powder with particle size range of 10-100 nanometers, directly put into 1 mol / L hydrogen peroxide solution, ultrasonic dispersion is uniform, adjust pH value to 10 with sodium hydroxide solution, decompose hydrogen peroxide by heating and boiling, volatilize excess water, obtain catalyst suspension liquid with solid content of 50%; take another polytetrafluoroethylene (PTFE) emulsion with solid content of 30%, mix with the nano catalyst suspension liquid, ultrasonic dispersion is uniform, obtain catalyst mixed emulsion; (3) The catalyst mixed emulsion is uniformly coated on the inner wall surface of the polytetrafluoroethylene blank, pre-dried at 90°C for 1.5 hours to remove water, heated to 120°C for 30 minutes, continuously heated to 300°C for 10 minutes, slowly cooled to room temperature in the furnace, obtain the driven friction stirring paddle 4 with surface loaded catalyst.

[0040] Example 5. This embodiment is a mechanical grinding catalytic oxidation stirring device 5 and its preparation method: The structure of the mechanical grinding catalytic oxidation stirring device 5 is the same as that of example 1, and the preparation method includes the preparation of the following key components and the installation according to the structure of the mechanical grinding catalytic oxidation stirring device, wherein the driving friction catalytic permeation paddle 5 is an alumina porous ceramic loaded with iron manganese carbon and barium titanate, and the driven friction stirring paddle 5 is a polytetrafluoroethylene loaded with barium titanate, and the preparation condition parameters are as follows: A: Preparation method of driving friction catalytic permeation paddle: (I) Take alumina porous ceramic with porosity of 60% and pore size range of 1-100 μm, which meets the technical requirements of national standard "GB / T 16533-1996, General Technical Conditions for Porous Ceramic Products", process the friction catalytic paddle into the required shape, soak in 12% sulfuric acid solution under micro-boiling state for 50 min, wash to neutral, then soak in 2% sodium hydroxide solution under micro-boiling state for 50 min, wash to near neutral, and dry for use; (II) Preparation of polyvinyl alcohol iron manganese mixed solution: take ferrous salt, ferric salt and divalent manganese salt in a molar ratio of 1:1:1, dissolve in 0.2 mol / L polyvinyl alcohol solution, and configure into iron manganese mixed solution containing 0.2 mol / L polyvinyl alcohol with total molar concentration of 2 mol / L; (III) Take barium titanate catalyst powder with particle size range of 10-100 nanometers, immerse in 1 mol / L hydrogen peroxide solution, ultrasonic dispersion is uniform, heat to 100°C for 60 min, add potassium hydroxide to make the concentration of potassium hydroxide in the solution 3 mol / L, obtain alkaline catalyst suspension liquid with nano catalyst of 4 g / L; (Four) the porous ceramic of step one is immersed in the iron-manganese mixed solution of step two, placed in a vacuum container, vacuumed to a relative pressure of ≤-0.09 MPa, pressure-kept for 60 min, the normal pressure is restored, and then dried at 65°C; the iron-manganese mixed solution is sprayed onto the porous ceramic until saturated absorption, and then dried; the spraying and drying are repeated until no more absorption is observed; finally, the dried porous ceramic is placed in a vacuum high-temperature furnace, vacuumed to a relative pressure of ≤-0.09 MPa, heated, and then heated to 900°C at a rate of 5°C / min, kept for 4 h, cooled to room temperature in the furnace, and then an iron-manganese carbon-loaded alumina porous ceramic sheet A is obtained; the alkaline barium titanate catalyst suspension obtained in step three is sprayed onto the outer surface of the iron-manganese carbon-loaded porous ceramic sheet A until saturated absorption, and then immersed for 14 h; the porous ceramic sheet is placed in a vacuum high-temperature furnace again, vacuumed to a relative pressure of -0.09 MPa, heated to 700°C at a rate of 4°C / min, and then kept for 1.5 h; the porous ceramic sheet is cooled to room temperature in the furnace, washed with water until neutral, and then an iron-manganese carbon and barium titanate-loaded alumina porous ceramic friction catalyst A5 is obtained; the porosity is 37%, which is not less than 30%, and thus the porous ceramic friction catalyst A5 is qualified. (Five) the friction catalyst A is installed on a hollow cone, the A sheets are arranged in a spiral upward, and a gap of 4 mm is left between the columns to form a spiral upward flow guide groove; a through hole with a diameter of 0.05 mm is opened on the wall of the hollow cone corresponding to the flow guide groove; after installation, a driven friction stirring paddle 5 is obtained. B: Method for loading catalyst on the inner surface of a polytetrafluoroethylene driven friction stirring paddle (1) A polytetrafluoroethylene material is taken, processed into a desired shape and size, and the surface is polished and cleaned with No. 100 sandpaper to obtain a polytetrafluoroethylene blank; (2) A barium titanate powder with a particle size range of 10-100 nm is directly added to a 0.5 mol / L hydrogen peroxide solution, ultrasonically dispersed, and then the pH value is adjusted to 11 with a sodium hydroxide solution; the hydrogen peroxide is decomposed by heating and boiling, and the excess water is volatilized to obtain a catalyst suspension with a solid content of 40%; a polytetrafluoroethylene (PTFE) emulsion with a solid content of 30% is mixed with the nanometer barium titanate suspension at a mass ratio of catalyst powder: PTFE of 1:5, and then ultrasonically dispersed to obtain a catalyst mixed emulsion; (3) The catalyst mixed emulsion is uniformly coated on the inner wall surface of the polytetrafluoroethylene blank, pre-dried at 80°C for 2 hours to remove water, heated to 120°C for 30 minutes, and then continuously heated to 300°C for 10 minutes; the furnace is slowly cooled to room temperature to obtain a driven friction stirring paddle 5 with a catalyst loaded on the surface.

[0041] Example 6 This example is a mechanical grinding catalytic oxidation stirring device 6 and a preparation method thereof: The structure of the mechanical grinding catalytic oxidation stirring device 6 is the same as that of Example 1, and the preparation method thereof comprises the preparation of the following key components and the installation according to the structure of the mechanical grinding catalytic oxidation stirring device as described, wherein the driving friction catalytic infiltration paddle 6 is a mullite porous ceramic loaded with iron manganese carbon and barium strontium titanate, and the driven friction stirring paddle 6 is polytetrafluoroethylene loaded with barium strontium titanate, and the preparation condition parameters are as follows: A: Preparation method of the driving friction catalytic infiltration paddle: (1) Take the mullite porous ceramic with a porosity of 50% and a pore size range of 0.2-20 μm, which meets the technical requirements of the national standard “GB / T 16533-1996, General Technical Conditions for Porous Ceramic Products”, process the friction catalytic paddle into the required shape, soak the paddle in a 10% sulfuric acid solution under a micro-boiling state for 60 min, wash with water until neutral, then soak the paddle in a 2% sodium hydroxide solution under a micro-boiling state for 30 min, wash with water until nearly neutral, and dry for use; (2) Preparation of polyvinyl alcohol iron manganese mixed solution: take ferrous salt, iron salt and divalent manganese salt in a molar ratio of 0.5:1:1, dissolve them in a 0.1 mol / L polyvinyl alcohol solution, and configure an iron manganese mixed solution with a total molar concentration of 1 mol / L containing 0.2 mol / L polyvinyl alcohol; (3) Take barium strontium titanate catalyst powder with a particle size range of 35-100 nanometers, immerse it in a 1 mol / L hydrogen peroxide solution, ultrasonic dispersion homogenization, heat to 100°C for 60 min, add potassium hydroxide to make the concentration of potassium hydroxide in the solution 3 mol / L, and obtain an alkaline catalyst suspension containing 5 g / L of nano catalyst; (4) Immerse the porous ceramic of step one in the iron manganese mixed solution of step two, place it in a vacuum container, vacuum to a relative pressure ≤-0.09 MPa, keep pressure for 60 min, restore normal pressure, take out and dry at 65°C, then spray the iron manganese mixed solution onto the porous ceramic until saturation, dry again, repeat the spraying, saturation, and drying at the same temperature until no more absorption, and finally dry and place in a vacuum high-temperature furnace, vacuum to a relative pressure ≤-0.09 MPa, heat, and increase the temperature to 900°C at a speed of 5°C / min, keep the temperature for 2 h, cool the furnace to room temperature, and obtain the mullite ceramic porous ceramic paddle loaded with iron manganese carbon; spray the alkaline barium strontium titanate catalyst suspension obtained in step three onto the outer surface of the mullite ceramic paddle loaded with iron manganese carbon until saturation, immerse for 24 h, place it in a vacuum high-temperature furnace again, vacuum to a relative pressure of -0.09 MPa, increase the temperature to 600°C at a speed of 3°C / min, keep the temperature for 2 h, cool the furnace to room temperature, wash with water until neutral, and obtain the mullite porous ceramic friction catalytic paddle 6 loaded with iron manganese carbon and barium strontium titanate, which has a porosity of 42%, not less than 30%, and is qualified; (Five) the step four friction catalytic installation on the hollow cone, the spiral upward distribution of the sheet, the column left 1mm gap, the formation of spiral upward guide groove, guide groove corresponding to the hollow cone wall opening diameter of 0.01mm through hole, after installation, get the initiative friction catalytic infiltration paddle 6; B: driven friction stir paddle is polytetrafluoroethylene when the inner surface load catalyst method: (1) take polytetrafluoroethylene material, processing into the required shape and size, clean surface with 100 grit sandpaper, get polytetrafluoroethylene blank; (2) take the particle size range 35-100 nanometer barium strontium titanate catalyst powder, directly into 0.5mol / L hydrogen peroxide solution, ultrasonic dispersion, adjust pH value to 10 with sodium hydroxide solution, heated to boiling decomposition of hydrogen peroxide, volatilize excess water, get the solid content of 60% catalyst suspension; According to the mass ratio of catalyst powder: PTFE is 1:6, take another 30% solid content of polytetrafluoroethylene (PTFE) emulsion, mixed with nano catalyst suspension, ultrasonic dispersion, get catalyst mixed emulsion; (3) the catalyst mixed emulsion, evenly coated on the inner wall surface of polytetrafluoroethylene blank, 100 DEG C pre drying 1h remove water, heating to 120 DEG C for 30 min, continue to heat to 300 DEG C for 10 min, slow cooling to room temperature in the furnace, get the surface load catalyst driven friction stir paddle 6.

[0042] Example 7 This embodiment is a mechanical grinding catalytic oxidation stirring device 7 and its preparation method: The structure of mechanical grinding catalytic oxidation stirring device 7 is the same as that of example 1, and its preparation method comprises the preparation of the following key components and the installation according to the structure of mechanical grinding catalytic oxidation stirring device, wherein the active friction catalytic infiltration paddle 7: the friction catalytic A is the zirconia porous ceramic loaded with iron manganese carbon and bismuth titanate; the driven friction stir paddle 7 is polytetrafluoroethylene loaded with barium titanate, and the preparation condition parameters are as follows: A: the preparation method of the active friction catalytic infiltration paddle: (I) take the zirconia porous ceramic, the porosity is 50%, the pore size range is 0.2-50μm, the technical requirements meet the provisions of the national standard "GB / T 16533-1996, general technical conditions for porous ceramic products", process the friction catalytic A of the required shape, soak in 10% sulfuric acid solution under the condition of micro boiling for 60 min, wash to neutral, then soak in 2% sodium hydroxide solution under the condition of micro boiling for 60 min, wash to near neutral, and dry for use; (ii) Preparation of polyvinyl alcohol iron manganese mixed solution: take ferrous salt, ferric salt and divalent manganese salt in a molar ratio of 1:1:1, dissolve in a 0.1 mol / L polyvinyl alcohol solution, and configure into an iron manganese mixed solution containing 0.1 mol / L polyvinyl alcohol with a total molar concentration of 1 mol / L; (iii) Take bismuth titanate catalyst powder with a particle size range of 60-100 nanometers, immerse it in a 0.1 mol / L hydrogen peroxide solution, ultrasonic dispersion homogenization, heat to 80°C for 30 minutes, add potassium hydroxide to make the potassium hydroxide concentration in the solution 1 mol / L, and obtain a basic catalyst suspension containing 2 g / L of nano catalyst; (iv) Immerse the porous ceramic of step (i) in the iron manganese mixed solution of step ii, place it in a vacuum container, vacuum to a relative pressure ≤-0.09 MPa, keep pressure for 30 minutes, restore normal pressure, take out and dry at 45°C, then spray the iron manganese mixed solution onto the porous ceramic until it is saturated, then dry again, repeat the spraying, saturation and drying until no more absorption is observed, and finally dry and place in a vacuum high-temperature furnace, vacuum to a relative pressure ≤-0.09 MPa, heat to 500°C at a rate of 3°C / min, keep temperature for 2h, cool in the furnace to room temperature, obtain the zirconia ceramic porous ceramic sheet loaded with iron manganese carbon, and spray the basic bismuth titanate catalyst suspension obtained in step iii onto the outer surface of the porous ceramic sheet loaded with iron manganese carbon until it is saturated, immerse for 12h, then place it in a vacuum high-temperature furnace again, vacuum to a relative pressure of -0.09 MPa, heat to 600°C at a rate of 3°C / min, keep temperature for 1h, cool in the furnace to room temperature, wash with water to neutral, obtain the zirconia ceramic friction catalyst loaded with iron manganese carbon and bismuth titanate, and detect the porosity to be 32% (not less than 30%), which is qualified; (v) Install the friction catalyst of step iv on a hollow cone, arrange the sheet in a spiral upward with a gap of 0.1mm between the columns to form a spiral upward flow channel, and open a through hole with a diameter of 0.01mm on the wall of the hollow cone corresponding to the flow channel, after installation, obtain the active friction catalyst impregnation paddle 7; B: Method for loading catalyst on the inner surface of polytetrafluoroethylene driven friction stirring paddle (1) Take polytetrafluoroethylene material, process it into the required shape and size, polish and clean the surface with 100 grit sandpaper, and obtain polytetrafluoroethylene blank; (2) Take the titanium barium catalyst powder with particle size range of 10-100 nanometers, directly put into 0.1 mol / L hydrogen peroxide solution, ultrasonic dispersion is uniform, adjust pH value to 10 with sodium hydroxide solution, decompose hydrogen peroxide by heating and boiling, volatilize excess water, get catalyst suspension liquid with solid content of 40%; Take another polytetrafluoroethylene (PTFE) emulsion with solid content of 20% and mix with the nano catalyst suspension liquid, ultrasonic dispersion is uniform, get catalyst mixed emulsion; (3) The catalyst mixed emulsion is evenly coated on the inner wall surface of the polytetrafluoroethylene blank, pre-dried at 80°C for 1 hour to remove water, heated to 120°C for 30 minutes, continue to heat to 280°C for 10 minutes, slowly cool to room temperature in the furnace, get the driven friction stirring paddle 7 with surface loaded catalyst.

[0043] Example 8 This embodiment is a mechanical grinding catalytic oxidation stirring device 8 and its preparation method: The structure of the mechanical grinding catalytic oxidation stirring device 8 is the same as that of example 1, and the preparation method includes the preparation of the following key components and the installation according to the structure of the mechanical grinding catalytic oxidation stirring device, wherein the driving friction catalytic permeation paddle 8 is a silicon nitride porous ceramic loaded with iron manganese carbon and strontium titanate, and the driven friction stirring paddle 8 is a polytetrafluoroethylene loaded with barium titanate, and the preparation condition parameters are as follows: A: Preparation method of driving friction catalytic permeation paddle: (I) Take silicon nitride porous ceramic with porosity of 60% and pore size range of 1-100 μm, which meets the technical requirements of national standard "GB / T 16533-1996, General Technical Conditions for Porous Ceramic Products", process the friction catalytic paddle into the required shape, soak in 15% sulfuric acid solution under micro-boiling state for 60 min, wash with water to neutral, then soak in 2% sodium hydroxide solution under micro-boiling state for 60 min, wash with water to near neutral, and dry for use; (II) Preparation of polyvinyl alcohol iron manganese mixed solution: take ferrous salt, iron salt and divalent manganese salt in a molar ratio of 1:1:1, dissolve in 0.3 mol / L polyvinyl alcohol solution, and configure into iron manganese mixed solution with total molar concentration of 2 mol / L and containing 0.2 mol / L polyvinyl alcohol; (III) Take strontium titanate catalyst powder with particle size range of 10-100 nanometers (mass ratio of 1:1), immerse in 1 mol / L hydrogen peroxide solution, ultrasonic dispersion is uniform, heat to 100°C for 60 min, add potassium hydroxide to make the concentration of potassium hydroxide in the solution 3 mol / L, get alkaline catalyst suspension liquid with nano catalyst of 5 g / L; (Four) the porous ceramic of step one is immersed in the iron-manganese mixed solution of step two, placed in a vacuum container, vacuumed to a relative pressure of ≤-0.09 MPa, pressure-kept for 60 min, the normal pressure is restored, taken out and dried at 65°C, the iron-manganese mixed solution is sprayed on the porous ceramic until saturated absorption, dried again, added dropwise again, saturated absorption, dried again at the same temperature, repeated spraying, saturated absorption and drying until no longer absorbed, finally dried and placed in a vacuum high-temperature furnace, vacuumed to a relative pressure of ≤-0.09 MPa, heated, and heated to 900°C at a rate of 5°C / min, kept for 4 h, cooled to room temperature in the furnace, to obtain the silicon nitride porous ceramic piece loaded with iron-manganese carbon; the alkaline strontium titanate catalyst suspension obtained in step three is sprayed on the outer surface of the porous ceramic piece loaded with iron-manganese carbon until saturated absorption, immersed for 24 h, placed in a vacuum high-temperature furnace again, vacuumed to a relative pressure of-0.09 MPa, heated to 800°C at a rate of 5°C / min, kept for 2 h, cooled to room temperature in the furnace, washed with water to neutral, to obtain the silicon nitride friction catalyst piece 8 loaded with iron-manganese carbon and strontium titanate, the porosity is 36% (not less than 30%), which is qualified; (Five) the friction catalyst piece of step four is installed on a hollow cone, the piece is arranged in a spiral upward, a gap of 5 mm is left between the columns to form a spiral upward flow guide groove, a through hole with a hole diameter of 0.2 mm is opened on the wall of the hollow cone corresponding to the flow guide groove, after installation, the active friction catalyst drug infiltration paddle 8 is obtained; B: method for loading catalyst on the inner surface of polytetrafluoroethylene when the driven friction stirring paddle is polytetrafluoroethylene (1) polytetrafluoroethylene material is taken, processed into a required shape and size, and the surface is polished and cleaned with No. 100 sandpaper to obtain a polytetrafluoroethylene blank; (2) barium titanate catalyst powder with a particle size range of 10-100 nm is taken, directly added into 1 mol / L hydrogen peroxide solution, ultrasonically dispersed uniformly, the pH value is adjusted to 11 with sodium hydroxide solution, the hydrogen peroxide is decomposed by heating and boiling, and the excess water is volatilized to obtain a catalyst suspension with a solid content of 60%; according to a mass ratio of catalyst powder: PTFE of 1:6, polytetrafluoroethylene (PTFE) emulsion with a solid content of 30% is taken and mixed with the nano-catalyst suspension, ultrasonically dispersed uniformly to obtain a catalyst mixed emulsion; (3) the catalyst mixed emulsion is uniformly coated on the inner wall surface of the polytetrafluoroethylene blank, pre-dried at 100°C for 2 hours to remove water, heated to 120°C for 30 min, continuously heated to 300°C for 20 min, and slowly cooled to room temperature in the furnace to obtain a driven friction stirring paddle 8 with a surface loaded with catalyst.

[0044] Application Example In this application example, the device of embodiments 1-8 is used to treat synthetic water samples and actual wastewater to test the performance of wastewater treatment. The treatment process is: using one of the mechanical grinding catalytic oxidation stirring devices 1-8 to start treating wastewater: The synthetic water sample is a 5mmol / L aqueous solution of perfluorooctanoic acid; the actual wastewater is landfill leachate and heat treatment wastewater, and the COD Cr values are 63100mg / L and 17200mg / L, respectively.

[0045] The wastewater sample to be treated is placed in the barrel body 31 of the support barrel 3, the pH value is adjusted, the height adjuster 321 is adjusted to make the active friction catalytic permeation paddle 1 and the driven friction stirring paddle 2 have a suitable gap, one of the selected oxidizing agent solutions, hydrogen peroxide, potassium persulfate, and potassium permanganate solution, is injected into the liquid tank 121 and enters the liquid cabin 12, the drive motor 334 is turned on, the drive wheel 335 is engaged with the transmission, the driven gear disc 15 rotates, the active friction catalytic permeation paddle 1 rotates towards the upward direction of the spiral guide groove 111, the height adjuster 321 is continuously adjusted, the rotation resistance adjuster 354 of the driven friction stirring paddle 2 is adjusted, so that the driven friction stirring paddle 2 obtains a certain speed difference through the resistance and the friction force of the active friction catalytic permeation paddle 1, and the wastewater to be treated is driven by the spiral upward guide groove 11 on the surface of the active friction catalytic permeation paddle 1 and the friction groove 20 on the inner wall of the driven friction stirring paddle 2 to rise between the active friction catalytic permeation paddle 1 and the driven friction stirring paddle 2, and diffuse in the friction catalytic A 11 hole, and finally discharged from the liquid outlet hole 22 on the driven friction stirring paddle 2 and flow back into the barrel to complete the cycle; during this process, the size of the pressure adjuster 1211 switch is adjusted to change the pressure in the liquid cabin 12, the oxidizing agent penetrates into the friction catalytic A 11 through the permeation pipe 13, reacts with the pollutants in the wastewater on the catalyst of the friction catalytic A, at the same time, due to the differential speed between the active friction catalytic permeation paddle 1 and the driven friction stirring paddle 2, the friction force of the outer surface of the active friction catalytic permeation paddle 1 and the friction catalytic A 11 and the inner surface of the driven friction stirring paddle 2 acts on the catalyst, wastewater and oxidizing agent, decomposes the organic matter in the wastewater, realizes the decomposition and mineralization of harmful substances in the wastewater, when the wastewater treatment reaches the standard, the valve of the liquid outlet pipe 311 is opened, and the wastewater is discharged, completing the wastewater treatment.

[0046] Device 1 wastewater treatment experiment: when using the mechanical grinding catalytic oxidation stirring device 1 of example 1 to treat the water sample, using potassium persulfate as the oxidizing agent, the mass ratio of m potassium persulfate: m COD Cr is 2:1, and the potassium persulfate is configured into a 0.1mol / L aqueous solution for use; Device 1 wastewater treatment control experiment: while using device 1 to treat wastewater, the same catalyst powder and oxidant as in friction catalysis A are used for the control experiment, i.e. using nano-barium titanate powder as the catalyst, the dosage is 2 g / L, the same amount of potassium persulfate solution is added, stirring at a speed of 100 r / min for 60 min, high-speed centrifugal separation at 10,000 r / min, and then the supernatant is directly measured.

[0047] Device 2 wastewater treatment experiment: while using the mechanical grinding catalytic oxidation stirring device 2 of Example 2 to treat the water sample, potassium persulfate is used as the oxidant, and the mass ratio m potassium persulfate: m COD Cr is 2:1, and the potassium persulfate is configured into a 0.1 mol / L aqueous solution for use; Device 2 wastewater treatment control experiment: while using device 2 to treat wastewater, the same catalyst powder and oxidant as in friction catalysis A are used for the control experiment, i.e. using nano-barium titanate powder as the catalyst, the dosage is 2 g / L, the same amount of potassium persulfate solution is added, stirring at a speed of 100 r / min for 60 min, high-speed centrifugal separation at 10,000 r / min, and then the supernatant is directly measured.

[0048] Device 3 wastewater treatment experiment: while using the mechanical grinding catalytic oxidation stirring device 3 of Example 3 to treat the water sample, hydrogen peroxide is used as the oxidant, and the mass ratio m H2O2: m COD Cr is 1:1, and the hydrogen peroxide is directly added for use in the form of a 30% mass concentration solution; Device 3 wastewater treatment control experiment: while using device 3 to treat wastewater, the same catalyst powder and oxidant as in friction catalysis A are used for the control experiment, i.e. using nano-barium titanate powder as the catalyst, the dosage is 2 g / L, the same amount of hydrogen peroxide solution is added, stirring at a speed of 100 r / min for 60 min, high-speed centrifugal separation at 10,000 r / min, and then the supernatant is directly measured.

[0049] Device 4 wastewater treatment experiment: while using the mechanical grinding catalytic oxidation stirring device 4 of Example 4 to treat the water sample, hydrogen peroxide is used as the oxidant, and the mass ratio m H2O2: m COD Cr is 1:1, and the hydrogen peroxide is directly added for use in the form of a 30% mass concentration solution, and at the same time, the pH value of the water sample is adjusted to 3.5 in advance, and ferrous sulfate is added in the original wastewater sample in a molar ratio n H2O2: Fe 2+ of 3:1, the ferrous sulfate is added and stirred uniformly, and then the wastewater sample is treated according to the treatment method; after treatment, high-speed centrifugal separation is performed at 10,000 r / min, the supernatant is taken, the pH value is adjusted to 6-7, and then it is left to stand for filtration, and the filtrate is measured; The device 4 handles wastewater control experiment: using the device 4 to handle wastewater experiment, using the same catalyst powder and the same oxidant of friction catalysis A to do control experiment, namely using nano barium titanate powder as catalyst, the adding amount is 2g / L, adjusting pH value 3.5, adding the same amount of hydrogen peroxide solution, and ferrous sulfate, using 100r / min speed stirring reaction 60min, 10000r / min high speed centrifugal separation, taking supernatant, adjusting pH value to 6-7 after static setting filtration, taking filtrate directly determination.

[0050] The device 5 handles wastewater experiment: using the mechanical grinding catalytic oxidation stirring device 5 of example 5 to handle water sample, using potassium permanganate as oxidant, according to the mass ratio m potassium permanganate: m COD Cr 3:1, using 0.1mol / L aqueous solution of potassium permanganate; The device 5 handles wastewater control experiment: using the device 5 to handle wastewater experiment, using the same catalyst powder and the same oxidant of friction catalysis A to do control experiment, namely using nano barium titanate powder as catalyst, the adding amount is 2g / L, adding the same amount of potassium permanganate solution, using 100r / min speed stirring reaction 60min, 10000r / min high speed centrifugal separation, taking supernatant directly determination.

[0051] The device 6 handles wastewater experiment: using the mechanical grinding catalytic oxidation stirring device 6 of example 6 to handle water sample, using potassium permanganate as oxidant, according to the mass ratio m potassium permanganate: m COD Cr 3:1, using 0.1mol / L aqueous solution of potassium permanganate; The device 6 handles wastewater control experiment: using the device 6 to handle wastewater experiment, using the same catalyst powder and the same oxidant of friction catalysis A to do control experiment, namely using nano barium titanate powder as catalyst, the adding amount is 2g / L, adding the same amount of potassium permanganate solution, using 100r / min speed stirring reaction 60min, 10000r / min high speed centrifugal separation, taking supernatant directly determination.

[0052] The device 7 handles wastewater experiment: using the mechanical grinding catalytic oxidation stirring device 7 of example 7 to handle water sample, using potassium persulfate as oxidant, according to the mass ratio m potassium persulfate: m COD Cr 2:1, using 0.1mol / L aqueous solution of potassium persulfate; The device 7 handles wastewater control experiment: while the device 7 handles wastewater experiment, the same catalyst powder and the same oxidant of rubbing catalysis A are used for control experiment, that is, the nano bismuth titanate powder is used as catalyst, the adding amount is 2g / L, the same amount of potassium persulfate solution is added, 100r / min speed stirring reaction is used for 60min, 10000r / min high speed centrifugal separation is used, and the supernatant is directly measured.

[0053] The device 8 handles wastewater experiment: when the mechanical grinding catalytic oxidation stirring device 8 of example 8 handles water sample, hydrogen peroxide is used as oxidant, the mass ratio mH2O2: mCOD Cr The device 8 handles wastewater control experiment: while the device 8 handles wastewater experiment, the same catalyst powder and the same oxidant of rubbing catalysis A are used for control experiment, that is, the nano bismuth titanate powder is used as catalyst, the adding amount is 2g / L, the same amount of potassium persulfate solution is added, 100r / min speed stirring reaction is used for 60min, 10000r / min high speed centrifugal separation is used, and the supernatant is directly measured.

[0054] The perfluorooctanoic acid concentration before and after treatment is determined by ultraviolet-visible spectrophotometry, the wastewater COD Cr Value is determined by the DR3900 type water quality analyzer of Hashi company, and the results are shown in Figure 7 .

[0055] Figure 7 The results can be seen that the device of the application is excellent in performance, whether the device handles perfluorooctanoic acid, landfill leachate or high-concentration heat-treated wastewater, the treatment capacity is much higher than that of the conventional catalytic oxidation method, the removal rate of perfluorooctanoic acid is 64~97%, the removal rate of landfill leachate (COD Cr Value) is 69~97%, and the removal rate of heat-treated wastewater (COD Cr Value) is 81~99%.​

Claims

1. A mechanical grinding and catalytic oxidation stirring device, characterized in that, The mechanical grinding catalytic oxidation stirring device includes an active friction catalytic infiltration paddle (1), a driven friction stirring paddle (2), and a support tank (3). The active friction catalytic infiltration paddle (1) is a hollow cone. Friction catalysts (11) are provided on the outer wall of the cone. Multiple rows of friction catalysts (11) are arranged spirally upward. The gaps between the rows form spiral upward guide channels (111). The spiral upward rotation direction of the guide channels (111) is opposite to the rotation direction of the active friction catalytic infiltration paddle (1). The guide channels (111) and the hollow cavity of the active friction catalytic infiltration paddle (1) are connected through the infiltration pipe (13). A driven friction stirring paddle (2) is installed outside the cone of the active friction catalytic infiltration paddle (1). The driven friction stirring paddle (2) has a bottom opening. The inner wall of the driven friction stirring paddle (2) is provided with a spirally rising friction groove (20). The friction groove (20) on the inner wall of the driven friction stirring paddle (2) is frictionally matched with the friction catalyst (11) on the outer wall of the active friction catalytic infiltration paddle (1). The spiral rotation directions of the friction groove (20) and the guide groove (111) on the outer wall of the active friction catalytic infiltration paddle (1) are opposite. The lower outer wall of the cone of the driven friction stirring paddle (2) is provided with stirring blades (21). Above the friction groove (20) is a stirring blade (21). A drain hole (22) penetrating the cylinder wall is provided; the active friction catalytic infiltration paddle (1) and the driven friction stirring paddle (2) are both set on the support barrel (3), and the friction gap between the active friction catalytic infiltration paddle (1) and the driven friction stirring paddle (2) is adjusted by the support set on the support barrel (3), thereby changing the friction force, and is adjusted in conjunction with the rotation resistance regulator (354) on the driven friction stirring paddle (2) to realize the rotational differential adjustment of the active friction catalytic infiltration paddle (1) and the driven friction stirring paddle (2).

2. The mechanical grinding catalytic oxidation stirring device according to claim 1, characterized in that, The friction catalyst plate (11) is formed by splicing multiple rows of friction catalyst plates in a spiral arrangement and hanging on the surface of a cone. In the direction of the cone's central axis, the gap between two rows of friction catalyst plates forms a spirally rising guide channel (111). The hollow cavity of the cone is a drug tank (12). A drug trough (121) is provided at the top of the drug tank (12). The drug tank (12) and the drug trough (121) are connected. The drug trough (121) is a sealed chamber with a pressure regulator (1211) on top. A plugged drug tank cleaning port (122) is provided at the bottom of the drug tank (12). The drug tank (12) and the guide channel (111) are connected by multiple small drug penetration pipes (13). The active friction catalyst drug penetration paddle (1) is provided with an inner paddle suspension disc beam (14) and a driven toothed disc (15) on the upper part.

3. The mechanical grinding catalytic oxidation stirring device according to claim 1, characterized in that, The driven friction stirring paddle (2) is an open cone with a spiral friction groove (20) on the inner wall of the cone. The starting point of the friction groove (20) is located at the lower opening of the cone and the ending point is located in the upper middle part of the cone wall. The upward rotation direction is consistent with the rotation direction of the active friction catalytic infiltration paddle (1). On the wall of the end of the friction groove, there is a drain hole (22) that penetrates the wall. The lower outer wall of the driven friction stirring paddle (2) is equipped with stirring blades (21) and the upper part is equipped with an outer paddle suspension disc beam (23).

4. The mechanical grinding catalytic oxidation stirring device according to claim 1, characterized in that, The support tank (3) includes a tank body (31) and a column support (32) set on the upper part of the tank body. The support (32) passes through the upper beam (33) and the lower beam (35). An upper suspension beam (34) is also set on the upper beam. The active friction catalytic infiltration paddle is fixed on the upper beam through the inner paddle suspension disc beam (14) and can rotate freely along the axis. The driven friction stirring paddle (2) is fixed on the lower beam through the outer paddle suspension disc beam (23) and can rotate freely along the axis. A height adjuster (321) is set between the support (32) and the upper beam (33) to adjust the height of the upper beam (33) to adjust the friction gap between the active friction catalytic infiltration paddle (1) and the driven friction stirring paddle (2). A drain pipe (311) with a valve is set at the lowest point of the tank body (31).

5. The mechanical grinding catalytic oxidation stirring device according to claim 2, characterized in that, The active friction catalytic infiltration paddle (1) is fixed to the upper beam (33) and lower suspension beam (34) of the support barrel (3) by the inner paddle suspension bearing (331) set under the inner paddle suspension disc beam (14), the inner paddle upper stabilizing bearing (332) and the inner paddle lower stabilizing bearing (333) on the outer wall, so that the active friction catalytic infiltration paddle (1) can rotate freely along its conical central axis. The upper beam (33) or the upper suspension beam (34) is equipped with a drive motor (334) and a drive wheel (335). The drive wheel (335) meshes with the driven gear disc (15) to drive the active friction catalytic infiltration paddle (1) to rotate.

6. The mechanical grinding and catalytic oxidation stirring device according to claim 2, characterized in that, The driven friction agitator (2) is fixed to the lower beam (35) of the support barrel (3) by the outer propeller suspension bearing (351) set under the outer propeller suspension disc beam (23), the outer propeller upper stabilizing bearing (352) and the outer propeller lower stabilizing bearing (353) on the outer wall, so that the driven friction agitator (2) can rotate freely along the central axis of the cone. A rotation resistance adjuster (354) that can adjust the rotation resistance of the driven friction agitator (2) is set on the outer propeller suspension disc beam (23).

7. The mechanical grinding catalytic oxidation stirring device according to claim 2, characterized in that, The tribocatalyst A (11) is made of a porous ceramic material loaded with iron, manganese, carbon and catalyst. The porous ceramic is one or more of alumina ceramic, mullite ceramic, zirconium oxide ceramic and silicon nitride ceramic. The driven friction agitator (2) is made of polytetrafluoroethylene and has a catalyst loaded on its inner surface; The supported catalyst is selected from one or two of barium titanate, strontium titanate, barium strontium titanate, and bismuth titanate.

8. A method for preparing a mechanical grinding catalytic oxidation stirring device, characterized in that, The preparation of the following components and the installation of the mechanical grinding catalytic oxidation stirring device according to any one of claims 1-7 specifically include the following steps: A: Preparation method of active triboelectric catalytic drug penetration paste: (i) Take porous ceramics with a porosity of 40-60% and a pore size range of 0.2-100μm. The technical requirements shall comply with the national standard "GB / T 16533-1996, General Technical Conditions for Porous Ceramic Products". Process them into friction catalyst plates of the required shape. Soak them in a 5-15% sulfuric acid solution under a slight boiling state for 30-60 minutes. Wash them with water until neutral. Then soak them in a 1-2% sodium hydroxide solution under a slight boiling state for 30-60 minutes. Wash them with water until near neutral. Dry them for later use. (II) Preparation of polyvinyl alcohol iron-manganese mixture: Take ferrous salt, ferric salt and divalent manganese salt in a molar ratio of (0.5-1):1:1 and dissolve them in a 0.1-0.3 mol / L polyvinyl alcohol solution to prepare an iron-manganese mixture containing 0.1-0.2 mol / L polyvinyl alcohol with a total molar concentration of 1-2 mol / L. (ii) Take catalyst powder with a particle size range of 10-100 nanometers, immerse it in 0.1-1 mol / L hydrogen peroxide solution, disperse and homogenize it by ultrasonication, activate it by heating at 80-100℃ for 30-60 min, add potassium hydroxide to make the potassium hydroxide concentration in the solution 1-3 mol / L, and obtain an alkaline catalyst suspension containing 2-5 g / L of nano-catalyst. (iv) Immerse the porous ceramic from step (i) in the iron-manganese mixture from step (ii), place it in a vacuum container, evacuate to a relative pressure ≤ -0.09 MPa, maintain pressure and let stand for 30-60 minutes, restore to normal pressure, remove and dry at 45-65℃, then spray the iron-manganese mixture onto the porous ceramic until it is saturated with absorption, dry again, add it dropwise again until saturated with absorption, dry at the same temperature, repeat the spraying, absorption saturation and drying process until no more absorption occurs, finally dry and place in a vacuum high-temperature electric furnace, evacuate to a relative pressure ≤ -0.09 MPa, heat at a rate of 3~5℃ / min The temperature is raised to 500-900℃ and calcined for 2-4 hours. The furnace is then cooled to room temperature to obtain a porous ceramic plate loaded with iron, manganese and carbon. The alkaline catalyst suspension obtained in step (III) is sprayed onto the outer surface of the porous ceramic plate loaded with iron, manganese and carbon until absorption saturation is achieved. The plate is then impregnated for 12-24 hours and placed in a vacuum high-temperature furnace again. The vacuum is evacuated to a relative pressure of -0.09MPa, and the temperature is raised to 600-800℃ at a rate of 3-5℃ / min. The plate is then activated for 1-2 hours and cooled to room temperature in the furnace. The plate is then washed with water until neutral to obtain a friction catalyst plate. If the porosity is not less than 30%, it is considered qualified. (v) Install the friction catalyst A from step (iv) onto the hollow cone. The A plates are arranged spirally upwards with a gap of 0.1-5mm between the rows to form a spiral upward guide channel. The hollow cone wall corresponding to the guide channel has a through hole with a diameter of 0.01-0.2mm. After installation, an active friction catalyst drug penetration slurry is obtained. B: Method for loading catalyst onto the inner surface when the driven friction impeller is made of polytetrafluoroethylene: (1) Take polytetrafluoroethylene material, process it into the required shape and size, and clean the surface with 100-grit sandpaper to obtain polytetrafluoroethylene blank; (2) Take catalyst powder with a particle size range of 10-100 nanometers, add it to a 0.1-1 mol / L hydrogen peroxide solution, disperse it evenly by ultrasonication, adjust the pH value to 10-11 with sodium hydroxide solution, heat and boil to decompose hydrogen peroxide, evaporate excess water, and obtain a catalyst suspension with a solid content of 40-60%; according to the mass ratio of catalyst powder:PTFE is 1:(4-6), take polytetrafluoroethylene emulsion with a solid content of 20-30% and mix it with the nano-catalyst suspension, disperse it evenly by ultrasonication, and obtain a catalyst mixed emulsion; (3) The catalyst mixture emulsion is evenly coated on the inner wall surface of the polytetrafluoroethylene blank, pre-drying at 80~100℃ for 1~2 hours to remove moisture, heating to 120℃ and holding for 30 minutes, then heating to 280~300℃ and holding for 10~20 minutes, and slowly cooling to room temperature in the furnace to obtain a driven friction stirring paddle with surface-loaded catalyst.

9. The application of the mechanical grinding catalytic oxidation stirring device according to any one of claims 1-7 for treating wastewater, characterized in that, Including the following application methods: The wastewater to be treated is placed in the tank (31) of the support tank (3), the pH value is adjusted, and the height regulator (321) is adjusted to adjust the gap between the active friction catalytic infiltration paddle (1) and the driven friction stirring paddle (2). The oxidant solution is injected into the liquid tank (121) and enters the liquid chamber (12). The drive motor (334) is turned on, and through the drive wheel (335), the driven toothed disc (15) rotates. The active friction catalytic infiltration paddle (1) moves towards the spiral guide channel (111) so that it rises. The direction is rotated, and the height adjuster (321) is adjusted so that the driven friction stirring paddle (2) comes into contact with the active friction catalytic infiltration paddle (1). Under the action of friction, the driven friction stirring paddle (2) also rotates, thereby agitating the wastewater to be treated in the cylinder. The rotation resistance adjuster (354) of the driven friction stirring paddle (2) is adjusted so that the driven friction stirring paddle (2) obtains a speed difference through the resistance and the friction force of the active friction catalytic infiltration paddle (1), and so that the wastewater to be treated is agitated by the active friction. Driven by the spirally rising guide groove (11) on the surface of the catalytic infiltration paddle (1) and the friction groove (20) on the inner wall of the driven friction stirring paddle (2), the catalytic infiltration paddle (1) rises along the gap between the two and diffuses within the holes of the friction catalyst (11). Finally, it is discharged through the drain hole (22) on the driven friction stirring paddle (2) and flows back into the tank, completing the cycle. During this process, the pressure regulator (1211) is adjusted to change the pressure in the drug tank (12), and the oxidant permeates into the friction catalyst (11) along the infiltration pipe (13). The catalyst reacts with pollutants in the wastewater on the catalyst of the friction catalyst A. At the same time, due to the difference in speed between the active friction catalyst infiltration paddle (1) and the driven friction stirring paddle (2), the friction force of the outer surface of the active friction catalyst infiltration paddle (1) and the inner surface of the driven friction stirring paddle (2) acts on the catalyst, wastewater and oxidant, decomposes the organic matter in the wastewater, and realizes the decomposition and mineralization of harmful substances in the wastewater. When the wastewater treatment meets the standards, the valve of the drain pipe (311) is opened and the wastewater is discharged to complete the wastewater treatment.

10. The application of the mechanical grinding catalytic oxidation stirring device according to claim 9 for wastewater treatment, characterized in that, The oxidizing agent is one or more of hydrogen peroxide, potassium persulfate, and potassium permanganate.

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