Vibration catalytic water treatment device and treatment method thereof

Abstract

The vibration catalytic water treatment device comprises a peristaltic pump, an analysis pump, a rotational flow mixer and spindle-shaped reaction cavities, the peristaltic pump and the analysis pump are both communicated with the rotational flow mixer, and the multiple sets of spindle-shaped reaction cavities are communicated in series end to end through circular flanges to form a Venturi tube structure; the cyclone mixer is communicated with an inlet of the spindle-shaped reaction cavity, a rotating sleeve is vertically and rotatably mounted at a middle wide opening in the spindle-shaped reaction cavity, a plurality of groups of composite flexible catalytic membrane assemblies are fixedly mounted in the middle of the rotating sleeve, and an injection pump is arranged on one side, close to the cyclone mixer, of the spindle-shaped reaction cavity; and two groups of ultrasonic vibrators are fixedly mounted on the outer sides of narrow openings on the two sides of each group of spindle-shaped reaction cavities. The device has the advantages that the device is integrated with a coupled structure, integrates the effects of hydrodynamic cavitation, ultrasonic cavitation, sound-induced inverse piezoelectric catalysis, flow-induced positive piezoelectric catalysis, contact electrification catalysis, friction piezoelectric type nano generator and the like, and enhances the water treatment effect.

Description

Technical Field

[0001] This invention relates to the field of water treatment technology, and in particular to a vibration catalytic water treatment device and its treatment method. Background Technology

[0002] Synergistic efficiency improvement in pollution and carbon reduction is a crucial strategy for ecological civilization construction in the new development stage and a key lever for promoting the comprehensive green transformation of economic and social development. By 2030, the total carbon emissions from the entire wastewater treatment industry will reach 365 million tons of CO2 equivalent, accounting for 3% of the national total carbon emissions. Therefore, synergistic control is required for water environment governance, necessitating optimized technological pathways and vigorous promotion of wastewater resource utilization. Guided by this, the new situation demands multi-faceted approach to wastewater treatment, including the synergistic treatment of multiple pollutants, the coupled application of multiple green technologies, and the comprehensive design of combined pollution removal capacity. This aims to save energy, reduce consumption, and contribute to achieving green and low-carbon development goals. Among these approaches, the development and design of technologies and equipment based on the synergistic effect of green catalysis and pollution removal capacity, particularly utilizing vibration catalysis derived from acoustic catalysis, is relatively rare. Summary of the Invention

[0003] The purpose of this invention is to provide a vibration catalytic water treatment device and its treatment method. Through an integrated coupled structure, it combines the effects of hydraulic cavitation, ultrasonic cavitation, acoustic inverse piezoelectric catalysis, flow-induced positive pressure electrocatalysis, contact electrocatalysis, and triboelectric nanogenerator, thereby enhancing the water treatment effect.

[0004] The above-mentioned technical objective of the present invention is achieved through the following technical solution: In summary, the present invention has the following beneficial effects: A vibration catalytic water treatment device and its treatment method are characterized by comprising a peristaltic pump, an analytical pump, a cyclone mixer, and a spindle-shaped reaction chamber. The peristaltic pump and the analytical pump are both connected to the cyclone mixer. The spindle-shaped reaction chamber has a narrow-ends-wide-middle structure, with an inlet and an outlet at each end. Multiple sets of spindle-shaped reaction chambers are arranged, connected end-to-end by circular flanges to form a Venturi tube structure. The outlet of the tail spindle-shaped reaction chamber is a main outlet. The cyclone mixer is connected to the inlet of the spindle-shaped reaction chamber. A rotating sleeve is vertically rotatably installed at the wide opening in the middle of the spindle-shaped reaction chamber. Multiple sets of composite flexible catalytic membrane components are fixedly installed in the middle of the rotating sleeve, and the composite flexible catalytic membrane components are arranged in a ring around the middle of the rotating sleeve. An injection pump is provided on one side of the spindle-shaped reaction chamber near the cyclone mixer. Two sets of ultrasonic transducers are fixedly installed on the outer sides of the narrow openings on both sides of each set of spindle-shaped reaction chambers.

[0005] Preferably, both the peristaltic pump and the analytical pump are automatically controlled for sample injection via a PLC controller.

[0006] Preferably, the composite flexible catalytic membrane assembly includes a modified PVDF membrane, a modified PTEF permeable membrane, a superelastic nickel-titanium memory metal sheet, and a polymer hollow tube. The superelastic nickel-titanium memory metal sheet is disposed between the modified PVDF membrane and the modified PTEF permeable membrane. The modified PVDF membrane and the modified PTEF permeable membrane are bonded together around their perimeters. The polymer hollow tube is distributed in a leaf vein pattern within the modified PVDF membrane and the modified PTEF permeable membrane. The tail end of the polymer hollow tube is connected to an insertable rigid tube and the inside of a rotating sleeve. The superelastic nickel-titanium memory metal sheet is also wound with copper wire.

[0007] Preferably, the modified PVDF membrane is selected from one of the following: iron-carbon based PVDF composite flexible catalytic membrane, iron-based PVDF composite flexible catalytic membrane, or PVDF-NCs composite flexible catalytic membrane.

[0008] Preferably, the preparation method of the iron-carbon-based PVDF composite flexible catalytic membrane is as follows: 1.0g of iron source ferric chloride, 3.0g of carbon source glucose, and 2.5g of precipitant urea are mixed evenly with 30mL of water, added to a 100mL reaction vessel, and hydrothermally heated at 200℃ for 12h to prepare an iron-based / hydrothermal carbon core-shell structure composite. Then, the composite is heat-treated at 800℃ under N2 to obtain reduced nano-iron-based / hydrothermal carbon. PVDF is added to a mixed solution of acetone and DMF in a volume ratio of 4:6, and after ultrasonic and magnetic stirring, the reduced nano-iron-based / hydrothermal carbon is added and ultrasonically mixed again to obtain a mixed spinning solution. The iron-carbon-based PVDF composite flexible catalytic membrane is then prepared by electrospinning.

[0009] Preferably, the preparation method of the iron-based PVDF composite flexible catalytic membrane is as follows: Ferroelectric stone is ground to a micro-nano particle size of 0.1 μm using a planetary ball mill, cleaned by ultrasonication, and the micro-nano ferroelectric stone is added to a PVDF / DMF mixture and ultrasonically mixed to obtain a mixed spinning solution. The iron-based PVDF composite flexible catalytic membrane is then prepared by electrospinning.

[0010] Preferably, the preparation method of the PVDF-NCs composite flexible catalytic membrane is as follows: 10g of melamine is placed in a crucible and calcined in air at 550℃ for 3h to obtain C3N4, with a heating rate of 5℃ / min. 2g of C3N4 and 0.5g of glucose are mixed and placed in a hydrothermal reactor at 180℃ overnight. After filtration, washing, and drying, the membrane is then heat-treated with N2 at 800℃ for 1h, with a heating rate of 4℃ / min, to obtain CN-HCs. The NCs are then subjected to ultrasonic dispersion to obtain a uniform membrane. Nanoscale NCs were prepared and added to a mixed solution of acetone and DMF in a volume ratio of 4:6. After ultrasonic and magnetic stirring for 1 hour, ultrasonically mixed PVDF was added and ultrasonically stirred for another 6 hours to obtain a mixed spinning solution. PVDF-NCs composite flexible catalytic membrane was prepared by electrospinning. The spinning parameters were as follows: voltage of 20 kV, extrusion speed of spinning solution of 8 µL / min, distance between needle and collecting roller of 13 cm, and rotation speed of collecting roller of 400 rpm.

[0011] Preferably, the modified PTEF breathable membrane is prepared as follows: 1.5g glucose, 1g FeCl3×6H2O, 1g urea and 0.2g hexadecyltrimethylammonium bromide are mixed and dissolved in 30mL of deionized water. The mixture can be sonicated for 3min to accelerate dissolution and mixing. Then, the PTFE base membrane is placed in the mixture and subjected to hydrothermal loading at 180℃ for 6h. Afterward, it is washed alternately with ethanol and deionized water, and then placed in an oven or vacuum drying oven at 70℃ to completely dry and generate PTFE-FC. Polydimethylsiloxane is then drop-coated onto the surface for encapsulation to construct a modified PTEF breathable membrane with superhydrophobicity and internal rapid molecular diffusion pathway.

[0012] Preferably, a hollow water outlet pipe is also provided inside the rotating sleeve, the insertable rigid pipe is connected to the hollow water outlet pipe, a wire connected to a copper wire is provided between the hollow water outlet pipe and the rotating sleeve, a water pumping pipe is provided outside each set of spindle-shaped reaction chambers, one end of the water pumping pipe is movably sealed to the hollow water outlet pipe, and a pumping pump is provided on the water pumping pipe.

[0013] A vibration-catalyzed water treatment method, characterized by comprising the following steps: S1, the liquid to be treated is fed into the cyclone mixer through a peristaltic pump, and the oxidant is fed into the cyclone mixer through an analytical pump. The PLC controller controls the injection volume of the liquid to be treated and the oxidant. Air bubbles are generated in the cyclone mixer and enter the spindle-shaped reaction chamber. S2: The mixture, including the solution to be treated, oxidant, and air bubbles, enters the spindle-shaped reaction chamber. An injection pump is used to control the flow rate. + or OH - Upon addition, a preliminary cavitation catalytic effect occurs first under the Venturi tube effect, and the catalytic effect is further enhanced by ultrasound. S3: When passing through the composite flexible catalytic membrane module, because the composite flexible catalytic membrane module contains a superelastic nickel-titanium memory metal sheet, the catalytic membrane is spread in the liquid phase by centrifugal force through a rotation design; S4: When an external voltage is applied through the copper wire, the deformation of the superelastic nickel-titanium memory metal sheet can be controlled due to the local current thermal effect, causing the membrane module to deform. Due to the inverse piezoelectric effect of PVDF and PTFE, the piezoelectric catalytic effect can be enhanced by external pressures such as ultrasound and water flow. When the external voltage is removed from the copper wire, the modified PVDF membrane, the modified PTEF breathable membrane and the superelastic nickel-titanium memory metal sheet form a triboelectric nanogenerator to recover kinetic energy. The weak current signal generated is used for water quality monitoring in the cavity. S5: The oxidant can enhance the piezoelectric catalytic effect of the modified PVDF membrane for the treatment of organic wastewater. At the same time, the high-molecular hollow hose inside the composite flexible catalytic membrane module can discharge the treated effluent and generated product gas through the hollow water outlet pipe in stages. S6: Most of the remaining liquid to be treated is extended through a series of spindle-shaped reaction chambers. At the connection point, the cavitation effect of the Venturi tube enhances the activity of the downstream reaction liquid. Finally, most of the liquid to be treated is discharged through the main outlet after continuous flow treatment.

[0014] The swirling mixing bubbler in this invention generates nanobubbles, which enhance the reaction effect of the system.

[0015] In this invention, the superelastic nickel-titanium memory metal sheet is wound with copper wire. Applying an external voltage can control the deformation and enhance the inverse piezoelectric effect. Removing the external voltage can couple the double-layer film to generate a triboelectric nanogenerator effect for kinetic energy recovery. The generated weak current signal is used for water quality monitoring in the cavity. In this invention, the hollow polymer hose inside the composite flexible catalytic membrane module can initially discharge the treated effluent and generated product gas through the hollow water outlet pipe.

[0016] In this invention, by connecting spindle-shaped reaction chambers in series, a Venturi tube structure can be achieved, thereby generating a hydraulic cavitation effect and enhancing the activity of the downstream reaction liquid.

[0017] This invention integrates the effects of hydraulic cavitation, ultrasonic cavitation, acoustic inverse piezoelectric catalysis, flow-induced positive pressure electrocatalysis, contact electrocatalysis, and triboelectric nanogenerator through an integrated coupled structure, thereby enhancing water treatment efficiency. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of the overall structure of the present invention; Figure 2 This is a partial structural diagram of the composite flexible catalytic membrane assembly of the present invention; Figure 3This is a schematic diagram of the overall structure of the composite flexible catalytic membrane module in this invention; Figure 4 This is a schematic diagram of the installation structure of the composite flexible catalytic membrane assembly and the rotating sleeve in this invention; In the diagram: 1-Analytical pump, 2-Peristaltic pump, 3-Swirl mixer, 4-PLC controller, 5-Injection pump, 6-Spindle-shaped reaction chamber, 7-Ultrasonic transducer, 8-Composite flexible catalytic membrane assembly, 9-Rotating sleeve, 10-Circular flange, 11-Water pumping pipe, 12-Main outlet, 13-Modified PVDF membrane, 14-Modified PTEF breathable membrane, 15-Superelastic nickel-titanium memory metal sheet, 16-Polymer hollow flexible tube, 17-Insertion rigid tube, 18-Copper wire, 19-Hollow outlet pipe, 20-Extraction pump. Detailed Implementation

[0019] The specific embodiments of the present invention will be further described below with reference to the accompanying drawings. These embodiments do not constitute a limitation on the present invention.

[0020] like Figures 1 to 4 The vibration catalytic water treatment device shown includes a peristaltic pump 2, an analytical pump 1, a cyclone mixer 3, and a spindle-shaped reaction chamber 6. Both the peristaltic pump 2 and the analytical pump 1 are connected to the cyclone mixer 3. The spindle-shaped reaction chamber 6 has a narrow-at-both-ends and wide-in-the-middle structure, with an inlet and an outlet at each end. Multiple sets of spindle-shaped reaction chambers 6 are arranged, connected in series at both ends by circular flanges 10 to form a Venturi tube structure. The outlet of the tail spindle-shaped reaction chamber 6 is a main outlet 12. The cyclone mixer 3 and the spindle-shaped reaction chamber 6... The inlet is connected, and a rotating sleeve 9 is vertically and rotatably installed in the middle of the wide opening of the spindle-shaped reaction chamber 6. Multiple sets of composite flexible catalytic membrane components 8 are fixedly installed in the middle of the rotating sleeve 9. The multiple sets of composite flexible catalytic membrane components 8 are in the form of a fan-shaped rotor. The composite flexible catalytic membrane components 8 are arranged in a ring around the middle of the rotating sleeve 9. An injection pump 5 is set on one side of the spindle-shaped reaction chamber 6 near the cyclone mixer 3. Two sets of ultrasonic transducers 7 are fixedly installed on the outer side of the narrow openings on both sides of each set of spindle-shaped reaction chamber 6. The peristaltic pump 2 and the analytical pump 1 are both automatically controlled by the PLC controller 4.

[0021] The composite flexible catalytic membrane module 8 includes a modified PVDF membrane 13, a modified PTEF breathable membrane 14, a superelastic nickel-titanium memory metal sheet 15, and a polymer hollow tube 16. The superelastic nickel-titanium memory metal sheet 15 is disposed between the modified PVDF membrane 13 and the modified PTEF breathable membrane 14. The modified PVDF membrane 13 and the modified PTEF breathable membrane 14 are bonded together around their perimeters. The polymer hollow tube 16 is distributed in a leaf vein pattern within the modified PVDF membrane 13 and the modified PTEF breathable membrane 14. The tail end of the polymer hollow tube 16 is connected to the insert-type rigid tube 17 and the inside of the rotating sleeve 9. The superelastic nickel-titanium memory metal sheet 15 is also wound with copper wire 18.

[0022] The modified PVDF membrane 13 is selected from one of the following: iron-carbon based PVDF composite flexible catalytic membrane, iron-based PVDF composite flexible catalytic membrane, or PVDF-NCs composite flexible catalytic membrane.

[0023] The preparation method of the iron-carbon based PVDF composite flexible catalytic membrane is as follows: 1.0g of iron source ferric chloride, 3.0g of carbon source glucose and 2.5g of precipitant urea are mixed evenly with 30mL of water and added to a 100mL reactor. The mixture is then hydrothermally heated at 200℃ for 12h to prepare an iron-based / hydrothermal carbon core-shell structure composite. Subsequently, the composite is heat-treated at 800℃ under N2 to obtain reduced nano-iron-based / hydrothermal carbon. PVDF is added to a mixed solution of acetone and DMF in a volume ratio of 4:6. After ultrasonic and magnetic stirring, the reduced nano-iron-based / hydrothermal carbon is added and ultrasonic mixing is continued to obtain a mixed spinning solution. The iron-carbon based PVDF composite flexible catalytic membrane is then prepared by electrospinning.

[0024] The preparation method of iron-based PVDF composite flexible catalytic membrane is as follows: Ferroelectric stone is ground to a micro-nano particle size of 0.1 μm using a planetary ball mill, cleaned by ultrasonication, and the micro-nano ferroelectric stone is added to a PVDF / DMF mixture. The mixture is then further ultrasonically mixed to obtain a mixed spinning solution. The iron-based PVDF composite flexible catalytic membrane is then prepared by electrospinning.

[0025] The preparation method of PVDF-NCs composite flexible catalytic membrane is as follows: 10g of melamine is placed in a crucible and calcined in air at 550℃ for 3h to obtain C3N4. The heating rate is 5℃ / min. 2g of C3N4 and 0.5g of glucose are mixed and placed in a hydrothermal reactor at 180℃ overnight. After filtration, washing, and drying, the membrane is then heat-treated with N2 at 800℃ for 1h at a heating rate of 4℃ / min to obtain CN-HCs. The NCs are then ultrasonically dispersed to obtain a uniform nano-coated membrane. The NCs were prepared and added to a mixed solution of acetone and DMF in a volume ratio of 4:6. After ultrasonic and magnetic stirring for 1 hour, ultrasonic PVDF was added and ultrasonic mixing was continued for 6 hours to obtain a mixed spinning solution. PVDF-NCs composite flexible catalytic membrane was prepared by electrospinning. The spinning parameters were as follows: voltage of 20 kV, extrusion speed of spinning solution of 8 µL / min, distance between needle and collecting roller of 13 cm, and rotation speed of collecting roller of 400 rpm.

[0026] The modified PTEF breathable membrane 14 is prepared as follows: 1.5g glucose, 1g FeCl3×6H2O, 1g urea and 0.2g hexadecyltrimethylammonium bromide are mixed and dissolved in 30mL of deionized water. The mixture can be sonicated for 3min to accelerate dissolution and mixing. Then, the PTFE base membrane is placed in the mixture and subjected to hydrothermal loading at 180℃ for 6h. Afterward, it is washed alternately with ethanol and deionized water, and then placed in an oven or vacuum drying oven at 70℃ to dry completely to generate PTFE-FC. Polydimethylsiloxane is then drop-coated onto the surface for encapsulation to achieve uniform distribution and high loading of fillers in the polymer, thus constructing a modified PTEF breathable membrane 14 with superhydrophobicity and internal rapid molecular diffusion pathway.

[0027] A hollow water outlet pipe 19 is also provided inside the rotating sleeve 9. An insertable rigid pipe 17 is connected to the hollow water outlet pipe 19. A wire connected to a copper wire 18 is provided between the hollow water outlet pipe 19 and the rotating sleeve 9. A water pumping pipe 11 is provided outside each set of spindle-shaped reaction chambers 6. One end of the water pumping pipe 11 is movably sealed to the hollow water outlet pipe 19. A pumping pump 20 is provided on the water pumping pipe 11.

[0028] A vibration-catalyzed water treatment method includes the following steps: S1, the liquid to be treated is fed into the cyclone mixer 3 through the peristaltic pump 2, and the oxidant is fed into the cyclone mixer 3 through the analytical pump 1. The PLC controller 4 controls the injection volume of the liquid to be treated and the oxidant. Air bubbles are generated in the cyclone mixer 3 and enter the spindle-shaped reaction chamber 6. S2, the mixture including the liquid to be treated, oxidant, and bubbles enters the spindle-shaped reaction chamber 6, and the injection pump 5 is used to control H + or OH - Upon addition, a preliminary cavitation catalytic effect occurs first under the Venturi tube effect, and the catalytic effect is further enhanced by ultrasound. S3, when passing through the composite flexible catalytic membrane module 8, because the composite flexible catalytic membrane module 8 contains a superelastic nickel-titanium memory metal sheet 15, the catalytic membrane is spread in the liquid phase by centrifugal force through rotation design. Due to the memory framework design, it is further beneficial to fix the shape of the catalytic membrane and spread in the liquid phase. Due to its component design, it will generate acoustic reverse piezocatalysis, flow-induced positive piezocatalysis and contact electrocatalysis coupling effect. S4, when an external voltage is applied through the copper wire, the deformation of the superelastic nickel-titanium memory metal sheet 15 can be controlled due to the local current thermal effect, causing the membrane module to deform. Due to the inverse piezoelectric effect of PVDF and PTFE, the piezoelectric catalytic effect can be enhanced by external pressure such as ultrasound and water flow. When the external voltage is removed from the copper wire, the modified PVDF membrane 13, the modified PTEF breathable membrane 14 and the superelastic nickel-titanium memory metal sheet 15 form a triboelectric piezoelectric nanogenerator to recover kinetic energy. The weak current signal generated is used for water quality monitoring in the cavity. The composite flexible catalytic membrane module 8 and the rotary tube analog water turbine can also achieve partial kinetic energy recovery under continuous flow, enhancing the current signal. S5, the oxidant can subsequently enhance the piezoelectric catalytic effect of the modified PVDF membrane 13 for the treatment of organic wastewater. At the same time, the high-molecular hollow hose 16 inside the composite flexible catalytic membrane module 8 can discharge the treated effluent and generated product gas through the hollow water outlet pipe 19 in stages. When the oxidant is persulfate, the iron-carbon-based PVDF composite flexible catalytic membrane not only generates and enhances the piezoelectric catalytic effect for the treatment of organic wastewater, but also generates hydrogen. Due to the combined configuration of the modified PTEF permeable membrane 14, the membrane can simultaneously achieve membrane effluent and hydrogen recovery for energy storage. When the oxidant is chlorite, the iron-carbon-based PVDF composite flexible catalytic membrane not only generates and enhances the piezoelectric catalytic effect for the treatment of organic wastewater, but also generates chlorine dioxide. The membrane can simultaneously achieve membrane effluent and chlorine dioxide recovery for in-situ disinfection and utilization. In addition, due to the doping effect, the series of piezoelectric catalytic effects occurring on the membrane surface can alleviate membrane fouling and extend the service life of the membrane module. S6, most of the remaining liquid to be treated is extended through the spindle-shaped reaction chamber 6 in series. At the connection point, the cavitation effect of the Venturi tube enhances the activity of the lower reaction liquid. Finally, most of the liquid to be treated is discharged through the main outlet 12 after continuous flow treatment.

[0029] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art can make various modifications or equivalent substitutions to the present invention within the scope of its essence and protection. Such modifications or equivalent substitutions should also be considered to fall within the protection scope of the present invention.

Claims

1. A vibration-catalyzed water treatment device and its treatment method, characterized in that, The system includes a peristaltic pump, an analytical pump, a cyclone mixer, and a spindle-shaped reaction chamber. Both the peristaltic pump and the analytical pump are connected to the cyclone mixer. The spindle-shaped reaction chamber has a narrow-at-both-ends, wide-in-the-middle structure, with an inlet and an outlet at each end. Multiple sets of spindle-shaped reaction chambers are connected in series via circular flanges to form a Venturi tube structure. The outlet of the tail spindle-shaped reaction chamber is a main water outlet. The cyclone mixer is connected to the inlet of the spindle-shaped reaction chamber. A rotating sleeve is vertically and rotatably installed at the wide opening in the middle of the spindle-shaped reaction chamber. Multiple sets of composite flexible catalytic membrane assemblies are fixedly installed in the middle of the rotating sleeve, and the composite flexible catalytic membrane assemblies are arranged in a ring around the middle of the rotating sleeve. An injection pump is located on one side of the spindle-shaped reaction chamber near the cyclone mixer. Two sets of ultrasonic transducers are fixedly installed on the outer sides of the narrow openings on both sides of each set of spindle-shaped reaction chambers.

2. The vibration catalytic water treatment device according to claim 1, characterized in that: Both the peristaltic pump and the analytical pump are automatically controlled for sample injection via a PLC controller.

3. The vibration catalytic water treatment device according to claim 1, characterized in that: The composite flexible catalytic membrane assembly includes a modified PVDF membrane, a modified PTEF permeable membrane, a superelastic nickel-titanium memory metal sheet, and a polymer hollow tube. The superelastic nickel-titanium memory metal sheet is disposed between the modified PVDF membrane and the modified PTEF permeable membrane. The modified PVDF membrane and the modified PTEF permeable membrane are bonded together around their perimeters. The polymer hollow tube is distributed in a leaf vein pattern within the modified PVDF membrane and the modified PTEF permeable membrane. The tail end of the polymer hollow tube is converged into an insertable rigid tube and inside a rotating sleeve. The superelastic nickel-titanium memory metal sheet is also wound with copper wire.

4. The vibration catalytic water treatment device according to claim 1, characterized in that: The modified PVDF membrane is selected from one of the following: iron-carbon based PVDF composite flexible catalytic membrane, iron-based PVDF composite flexible catalytic membrane, or PVDF-NCs composite flexible catalytic membrane.

5. The vibration catalytic water treatment device according to claim 4, characterized in that: The preparation method of the iron-carbon based PVDF composite flexible catalytic membrane is as follows: 1.0g of iron source ferric chloride, 3.0g of carbon source glucose and 2.5g of precipitant urea are mixed evenly with 30mL of water, added to a 100mL reaction vessel, and hydrothermally heated at 200℃ for 12h to prepare an iron-based / hydrothermal carbon core-shell structure composite. Then, the composite is heat-treated at 800℃ under N2 to obtain reduced nano-iron-based / hydrothermal carbon. PVDF is added to a mixed solution of acetone and DMF in a volume ratio of 4:6, and after ultrasonic and magnetic stirring, the reduced nano-iron-based / hydrothermal carbon is added and ultrasonically mixed again to obtain a mixed spinning solution. The iron-carbon based PVDF composite flexible catalytic membrane is then prepared by electrospinning.

6. The vibration catalytic water treatment device according to claim 1, characterized in that: The preparation method of the iron-based PVDF composite flexible catalytic membrane is as follows: Ferroelectric stone is ground to a micro-nano particle size of 0.1 μm using a planetary ball mill, cleaned by ultrasonication, and the micro-nano ferroelectric stone is added to a PVDF / DMF mixture. The mixture is then further ultrasonically mixed to obtain a mixed spinning solution. The iron-based PVDF composite flexible catalytic membrane is then prepared by electrospinning.

7. The vibration catalytic water treatment device according to claim 1, characterized in that: The preparation method of the PVDF-NCs composite flexible catalytic membrane is as follows: 10g of melamine is placed in a crucible and calcined in air at 550℃ for 3h to obtain C3N4, with a heating rate of 5℃ / min. 2g of C3N4 and 0.5g of glucose are mixed and placed in a hydrothermal reactor at 180℃ overnight. After filtration, washing, and drying, the membrane is then heat-treated with N2 at 800℃ for 1h, with a heating rate of 4℃ / min, to obtain CN-HCs. The NCs are then ultrasonically dispersed to obtain a uniform and... Nanoscale NCs were prepared and added to a mixed solution of acetone and DMF in a volume ratio of 4:

6. After ultrasonic and magnetic stirring for 1 hour, ultrasonically mixed PVDF was added and ultrasonically stirred for another 6 hours to obtain a mixed spinning solution. PVDF-NCs composite flexible catalytic membrane was prepared by electrospinning. The spinning parameters were as follows: voltage of 20 kV, extrusion speed of spinning solution of 8 µL / min, distance between needle and collecting roller of 13 cm, and rotation speed of collecting roller of 400 rpm.

8. The vibration catalytic water treatment device according to claim 1, characterized in that: The modified PTEF breathable membrane is prepared as follows: 1.5g glucose, 1g FeCl3×6H2O, 1g urea and 0.2g hexadecyltrimethylammonium bromide are mixed and dissolved in 30mL of deionized water. The mixture can be sonicated for 3min to accelerate dissolution and mixing. Then, the PTFE base membrane is placed in the mixture and subjected to hydrothermal loading at 180℃ for 6h. Afterward, it is washed alternately with ethanol and deionized water, and then placed in an oven or vacuum drying oven at 70℃ to completely dry and generate PTFE-FC. Polydimethylsiloxane is then drop-coated onto the surface for encapsulation to construct a modified PTEF breathable membrane with superhydrophobicity and internal rapid molecular diffusion pathway.

9. The vibration catalytic water treatment device according to claim 3, characterized in that: A hollow water outlet pipe is also provided inside the rotating sleeve. The insertable rigid pipe is connected to the hollow water outlet pipe. A wire connected to a copper wire is provided between the hollow water outlet pipe and the rotating sleeve. A water pumping pipe is provided outside each set of spindle-shaped reaction chambers. One end of the water pumping pipe is movably sealed to the hollow water outlet pipe. A pumping pump is provided on the water pumping pipe.

10. A vibration-catalyzed water treatment method, characterized in that: Includes the following steps: S1, the liquid to be treated is fed into the cyclone mixer through a peristaltic pump, and the oxidant is fed into the cyclone mixer through an analytical pump. The PLC controller controls the injection volume of the liquid to be treated and the oxidant. Air bubbles are generated in the cyclone mixer and enter the spindle-shaped reaction chamber. S2: the mixed solution including the liquid to be treated, oxidant and bubbles enters the spindle-shaped reaction cavity, and the injection pump is used to control the H + or OH - The addition firstly causes a preliminary cavitation catalysis effect under the Venturi effect, and the catalysis effect is further enhanced under the ultrasonic effect; S3: When passing through the composite flexible catalytic membrane module, because the composite flexible catalytic membrane module contains a superelastic nickel-titanium memory metal sheet, the catalytic membrane is spread in the liquid phase by centrifugal force through a rotation design; S4: When an external voltage is applied through the copper wire, the deformation of the superelastic nickel-titanium memory metal sheet can be controlled due to the local current thermal effect, causing the membrane module to deform. Due to the inverse piezoelectric effect of PVDF and PTFE, the piezoelectric catalytic effect can be enhanced by external pressures such as ultrasound and water flow. When the external voltage is removed from the copper wire, the modified PVDF membrane, the modified PTEF breathable membrane and the superelastic nickel-titanium memory metal sheet form a triboelectric nanogenerator to recover kinetic energy. The weak current signal generated is used for water quality monitoring in the cavity. S5: The oxidant can enhance the piezoelectric catalytic effect of the modified PVDF membrane for the treatment of organic wastewater. At the same time, the high-molecular hollow hose inside the composite flexible catalytic membrane module can discharge the treated effluent and generated product gas through the hollow water outlet pipe in stages. S6: Most of the remaining liquid to be treated is extended through a series of spindle-shaped reaction chambers. At the connection point, the cavitation effect of the Venturi tube enhances the activity of the downstream reaction liquid. Finally, most of the liquid to be treated is discharged through the main outlet after continuous flow treatment.

Images