Electrocatalytic filtration membranes for removing bromate from water: preparation methods, apparatus, and applications.

Abstract

This invention belongs to the field of water treatment technology, specifically an electrocatalytic filter membrane for removing bromate from water, its preparation method, apparatus, and application. S1: Carbon nanotube sponge is cut or selected as the substrate, with a size of 20×20×1mm. Simultaneously, aminophthalocyanine copper (purity ≥95%), binder (Nafion 117 solution, concentration 5wt%), and organic solvent N,N-dimethylformamide (DMF, purity ≥99.8%) are prepared. S2: The aminophthalocyanine copper powder and Nafion 117 solution are mixed in DMF solvent using an ultrasonic device at room temperature to form a uniform conductive ink. The electrocatalytic filter membrane prepared by this method has a copper loading of 1.0~3.0 wt%, and the bromate removal rate reaches over 96%. In application, the current density of the electrocatalytic filter membrane is 2~5 mA / cm². 2 Energy consumption is as low as 0.75 kWh / g BrO3. ‑ It operates stably for 120 hours and is suitable for water bodies with bromate concentrations of 0.2~5.0 mg / L. The direct reduction mechanism avoids the problem of organic matter quenching and solves the technical problem of "high energy consumption and poor stability of electrocatalytic materials in reducing bromate".

Description

Technical Field

[0001] This invention belongs to the field of water treatment technology, specifically an electrocatalytic filter membrane for removing bromate from water, its preparation method, apparatus, and application. Background Technology

[0002] Bromate is a common disinfection byproduct, primarily originating from ozone oxidation or advanced oxidation processes in water treatment plants. Bromate exhibits both genotoxic and non-genotoxic properties and was listed as a possible human carcinogen in the 1990s. The World Health Organization (WHO) stipulates that the concentration of bromate in drinking water must not exceed 10 μg / L. However, the bromide ion content in natural freshwater typically ranges from 10 to 1000 μg / L, making it highly susceptible to bromate exceeding the standard. Therefore, developing green and efficient bromate removal methods is of great significance for ensuring the safety of drinking water for residents.

[0003] Compared to traditional physical, chemical, and biological treatment technologies, electrochemical reduction technology has significant advantages such as high removal efficiency, small footprint, high degree of automation, and low secondary pollution. Therefore, it has received widespread attention in the fields of surface water, source water, and drinking water treatment in recent years. Existing electrode materials for the electroreduction of bromate mainly rely on indirect electron transfer, i.e., electrolysis of water to generate active hydrogen, which reduces bromate. However, the active hydrogen generated in this process may be quenched by organic matter in the water, and the instability of the electrocatalytic material may lead to a decrease in electroreduction efficiency. Furthermore, the large amount of electrical energy consumed in the electroreduction process is another significant obstacle restricting the practical application of this technology. Therefore, this invention provides an electrocatalytic filter membrane for removing bromate from water, its preparation method, apparatus, and applications. Summary of the Invention

[0004] In order to overcome the shortcomings of the prior art, at least one technical problem raised in the background art is solved.

[0005] The technical solution adopted by this invention to solve its technical problem is: the preparation method of the electrocatalytic filter membrane for removing bromate from water according to this invention, the method comprising the following steps:

[0006] S1: Cut or select carbon nanotube sponge as the substrate, with a size of 20×20×1mm. At the same time, prepare aminophthalocyanine copper (purity ≥95%), adhesive (Nafion 117 solution, concentration 5wt%), and organic solvent N,N-dimethylformamide (DMF, purity ≥99.8%).

[0007] S2: Mix the aminophthalocyanine copper powder with Nafion 117 solution in DMF solvent and use an ultrasonic device to mix at room temperature to form a uniform conductive ink. Completely immerse the prepared carbon nanotube sponge in the conductive ink for 8-8.5 hours to ensure that the sponge is in full contact with the ink.

[0008] S3: Remove the soaked sponge from the ink, wash it repeatedly with pure DMF solvent to remove excess ink and unloaded residue, place the washed sponge in a vacuum drying oven and dry it under controlled temperature and time to finally obtain aminophthalocyanine copper nanosponges (i.e. electrocatalytic filter membranes).

[0009] The method also includes the following steps:

[0010] A1: By injecting DMF solvent into the upper shell through the inlet tube, the DMF solvent fills the lower and upper shells. Use tweezers to place the sponge between a pair of flexible plates. Use the drive spring to push the flexible plates to clamp the sponge.

[0011] A2: Start the motor so that it drives the stirring blade to rotate. At this time, the DMF solvent will be stirred to wash the sponge. At the same time, the first and second magnetic blocks drive the upper shell to shake, so that the DMF solvent can be sprayed onto the sponge from the round hole.

[0012] A3: After the first wash is completed, the DMF solvent is discharged from the outlet pipe, and new DMF solvent is injected into the upper shell from the inlet pipe to continue washing the sponge repeatedly.

[0013] An electrocatalytic filter membrane for removing bromate from water is prepared by the above-described method. The electrocatalytic filter membrane comprises carbon nanotube sponge, aminophthalocyanine copper, binder, organic solvent, and DMF solvent. The binder is a Nafion 117 solution with a concentration of 5 wt%.

[0014] The ratio of aminophthalocyanine copper to binder is 100~200 g / L by mass / volume. The amount of DMF solvent used is 9 mL-11 mL to meet the requirements of ink preparation. The purity of aminophthalocyanine copper needs to be ≥95%. The organic solvent is N,N-dimethylformamide with a purity of ≥99.8%.

[0015] An apparatus for preparing an electrocatalytic filter membrane for removing bromate from water is provided. The apparatus is used to prepare the aforementioned electrocatalytic filter membrane. The cleaning device includes a lower shell and an upper shell. The bottom end of the lower shell is connected to a pair of liquid outlet pipes, and the top end of the upper shell is connected to a liquid inlet pipe. A placement groove is provided at the top end of the upper shell. A hollow block is fixedly connected to the bottom surface of the inner wall of the lower shell. A rotating shaft is rotatably connected to the top end of the hollow block. A stirring blade is fixedly connected to the outer wall of the rotating shaft. A motor for driving the rotating shaft to rotate is installed inside the hollow block.

[0016] The lower housing has a sliding groove, the upper housing is disposed in the sliding groove, a pair of connecting plates are fixedly connected to the inner wall of the upper housing, a first magnetic block is fixedly connected to the bottom surface of the connecting plate, a second magnetic block that repels the first magnetic block is fixedly connected to the top surface of the stirring blade, a set of return springs are fixedly connected between the bottom surface of the upper housing and the bottom surface of the inner wall of the sliding groove, and a clamping assembly for clamping the sponge is provided inside the upper housing.

[0017] The bottom surface of the upper housing is provided with a connecting groove that communicates with the sliding groove, and the inner wall of the upper housing is provided with multiple sets of circular holes that communicate with the connecting groove. The upper housing and the inner wall of the sliding groove are in a sealed sliding connection.

[0018] The clamping assembly includes a pair of slide rods slidably connected to the side wall of the upper housing. A rectangular plate is fixedly connected to the top surface of the inner wall of the upper housing. The slide rods pass through the rectangular plate. A connecting ring is fixedly connected to the surface of the slide rods. A drive spring is fixedly connected between the connecting ring and the rectangular plate. A flexible plate is fixedly connected to the side of the slide rods near the placement groove. Multiple sets of protrusions are located on the side of the flexible plate away from the slide rods.

[0019] Application of an electrocatalytic filter membrane for removing bromate from water, wherein the electrocatalytic filter membrane is used to remove bromate from groundwater.

[0020] The beneficial effects of this invention are as follows:

[0021] 1. The electrocatalytic filter membrane prepared by the method of this invention has a copper loading of 1.0~3.0 wt%, and a bromate removal rate of up to 96% or more. The electrocatalytic filter membrane operates at a current density of 2~5 mA / cm² during application. 2 Energy consumption is as low as 0.75 kWh / g BrO3. ⁻ It operates stably for 120 hours and is suitable for water bodies with bromate concentrations of 0.2~5.0 mg / L. The direct reduction mechanism avoids the problem of organic matter quenching and solves the technical problem of "high energy consumption and poor stability of electrocatalytic materials in reducing bromate".

[0022] 2. In this invention, DMF solvent is injected into the upper shell through the inlet pipe, and then the liquid fills the lower and upper shells. Then, the ink-soaked sponge is placed into the upper shell through the placement tank using tweezers. At this time, the DMF solvent soaks the sponge. Then, the motor is started, which drives the stirring blade to rotate. At this time, the DMF solvent is stirred and washes the sponge. Attached Figure Description

[0023] The invention will now be further described with reference to the accompanying drawings.

[0024] Figure 1 and Figure 2 This is a flowchart of the method in this invention;

[0025] Figure 3 and Figure 4 Microscopic morphology of the electrocatalytic filter membrane prepared by the method of the present invention;

[0026] Figure 5 The carbon nanotube sponge substrate without aminophthalocyanine copper in Comparative Example 1 of this invention;

[0027] Figure 6 The bromate reduction curve within 2 hours under the operating conditions provided by this invention;

[0028] Figure 7 The diagram shows the efficiency of electrocatalytic reduction of bromate under the operating conditions provided in Application Example 1 of this invention.

[0029] Figure 8 The diagram shows the electrocatalytic reduction efficiency and power consumption of bromate under the operating conditions provided in Application Example 2 of this invention.

[0030] Figure 9 The diagram shows the efficiency of electrocatalytic reduction of bromate under the operating conditions provided in Application Example 3 of this invention.

[0031] Figure 10 This is a schematic diagram of the cleaner in this invention;

[0032] Figure 11 This is a schematic diagram of the internal structure of the upper and lower shells in this invention;

[0033] Figure 12 This is a schematic diagram of the clamping component in this invention.

[0034] In the diagram: 1. Lower shell; 2. Upper shell; 3. Placement slot; 4. Inlet pipe; 5. Outlet pipe; 6. Hollow block; 7. Motor; 8. Rotating shaft; 9. Stirring blade; 10. Slide groove; 11. Connecting groove; 12. Round hole; 13. Connecting plate; 14. First magnetic block; 15. Second magnetic block; 16. Slide rod; 17. Connecting ring; 18. Rectangular plate; 19. Flexible plate; 20. Protrusion; 21. Drive spring. Detailed Implementation

[0035] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below in conjunction with specific embodiments.

[0036] Example 1: As Figures 1 to 9 As shown in the embodiment of the present invention, the method for preparing an electrocatalytic filter membrane for removing bromate from water includes the following steps:

[0037] S1: Cut or select carbon nanotube sponge as the substrate, with a size of 20×20×1mm. At the same time, prepare aminophthalocyanine copper (purity ≥95%), adhesive (Nafion 117 solution, concentration 5wt%), and organic solvent N,N-dimethylformamide (DMF, purity ≥99.8%).

[0038] S2: Mix the aminophthalocyanine copper powder with Nafion 117 solution in DMF solvent and use an ultrasonic device to mix at room temperature to form a uniform conductive ink. Completely immerse the prepared carbon nanotube sponge in the conductive ink for 8-8.5 hours to ensure that the sponge is in full contact with the ink.

[0039] S3: Remove the soaked sponge from the ink, wash it repeatedly with pure DMF solvent to remove excess ink and unloaded residue, place the washed sponge in a vacuum drying oven and dry it under controlled temperature and time to finally obtain aminophthalocyanine copper nanosponges (i.e. electrocatalytic filter membranes).

[0040] The method also includes the following steps:

[0041] A1: By injecting DMF solvent into the upper housing 2 through the inlet pipe 4, the DMF solvent fills the lower housing 1 and the upper housing 2. Use tweezers to place the sponge between a pair of flexible plates 19. Use the drive spring 21 to push the flexible plates 19 to clamp the sponge.

[0042] A2: Start motor 7, so that motor 7 drives stirring blade 9 to rotate. At this time, DMF solvent will be stirred to wash the sponge. At the same time, the upper shell 2 is driven to shake by the first magnetic block 14 and the second magnetic block 15, so that DMF solvent can be sprayed onto the sponge from the round hole 12.

[0043] A3: After the first wash is completed, the DMF solvent is discharged from the outlet pipe 5, and new DMF solvent is injected into the upper shell 2 from the inlet pipe 4 to continue washing the sponge repeatedly.

[0044] Step 1, Preparation of aminophthalocyanine copper conductive ink: 100 mg of 95% pure aminophthalocyanine copper powder, 500 μL of 5 wt% pure Nafion 117 solution and 10 mL of 99.8% pure N,N-dimethylformamide solution were ultrasonically mixed at room temperature for 30 min to obtain aminophthalocyanine copper conductive ink.

[0045] Step 2, Preparation of aminophthalocyanine copper nanosponges: A 20×20×1 mm carbon nanotube sponge was immersed in the aminophthalocyanine copper conductive ink obtained in step (1). After 8 hours, it was removed, washed with a 99.8% pure N,N-dimethylformamide solution, and then vacuum-dried at 40°C for 12 hours to obtain aminophthalocyanine copper nanosponges, which is the electrocatalytic filter membrane for bromate removal in water. The obtained aminophthalocyanine copper nanosponges were structurally characterized, and the results are shown in the appendix of the instruction manual. Figure 3 As shown in the figure, copper aminophthalocyanine is uniformly loaded on the surface of carbon nanotubes.

[0046] The electrocatalytic filter membrane prepared using the method was used as the cathode, and the platinum mesh as the anode. The water permeable area of ​​the electrocatalytic membrane was 12 × 12 mm, and the filtered water flux was 83.33 L / (m²). 2 The working current density for the electrocatalytic reduction of bromate via the filter membrane is 2 mA / cm² (h). 2 At a current density of 1 mg·L -1 (with BrO3) - (Calculate) a sodium bromate solution. Experimental results are attached to the instruction manual. Figure 5 As shown in the figure, within 2 hours, compared with the carbon nanotube sponge, the carbon nanotube sponge loaded with aminophthalocyanine copper showed better performance against BrO3. - The removal efficiency was increased by 3.89 times.

[0047] Comparative Example 1:

[0048] Carbon nanotube sponge substrate without aminophthalocyanine copper loading. Characterization results are attached to the instruction manual. Figure 6 As shown in the figure, the carbon nanotube fibers in the unloaded carbon nanotube sponge are smaller in diameter compared to the carbon nanotube sponge loaded with aminophthalocyanine copper.

[0049] The electrochemical reduction of bromate by carbon nanotube sponge substrate and aminophthalocyanine copper nanosponges within 2 h was compared, and the following steps were performed:

[0050] The carbon nanotube sponge provided in Comparative Example 1 and the electrocatalytic filter membrane prepared in the examples were used as cathodes and platinum mesh as anodes, respectively. The water permeable area of ​​the electrocatalytic membrane was 12 × 12 mm, and the filtered water flux was 83.33 L / (m²). 2 The working current density for the electrocatalytic membrane reduction of bromate is 2 mA / cm². 2 Filtering at a current density containing 10 mmol / L sodium sulfate and 1 mg·L⁻¹ -1 (with BrO3) -(Calculation) A sodium bromate solution. Sodium sulfate, as a strong electrolyte, can increase the ion concentration of the solution, thereby increasing the electrolyte conductivity, reducing the internal resistance of the solution, ensuring efficient current transfer between the electrode and the solution, and thus improving the efficiency and accuracy of electrochemical experiments. Experimental results are shown in […]. Figure 5 As shown in the figure, the electrochemical reduction removal rates of bromate by carbon nanotube sponge and aminophthalocyanine copper nanosponge within 2 h were 24.71% and 96.25%, respectively.

[0051] Comparative Example 2:

[0052] The preparation method of the electrocatalytic filter membrane used for removing bromate from groundwater in this comparative example is carried out according to the following steps:

[0053] Preparation of aminophthalocyanine copper conductive ink: 50, 100, and 150 mg of 95% pure aminophthalocyanine copper powder, 500 μL of 5 wt% Nafion 117 solution, and 10 mL of 99.8% pure N,N-dimethylformamide solution were ultrasonically mixed at room temperature for 30 min to obtain aminophthalocyanine copper conductive ink. The remaining steps were the same as in step two. The copper loading on the surface of the prepared aminophthalocyanine copper nanotube sponge was 1 wt%, 3 wt%, and 4 wt%, respectively.

[0054] Carbon nanotube sponges and the electrocatalytic filter membrane prepared in the examples were used as cathodes, and platinum mesh as anodes, respectively. The water permeable area of ​​the electrocatalytic membrane was 12 × 12 mm, and the filtered water flux was 83.33 L / (m²). 2 The working current density for the electrocatalytic reduction of bromate via the filter membrane is 2 mA / cm² (h). 2 Filtering at a current density containing 10 mmol / L sodium sulfate and 1 mg·L⁻¹ -1 (with BrO3) - (Calculate) a solution of sodium bromate.

[0055] The experimental results are shown in Figure 6 As shown in the figure, the electrochemical reduction removal rates of bromate by 1 wt%, 3 wt%, and 4 wt% aminophthalocyanine copper nanosponges within 2 h were 86.33%, 96.25%, and 95.69%, respectively.

[0056] Application Example 1:

[0057] Using the electrocatalytic filter membrane prepared in Example 1 as the cathode and a platinum sheet as the anode, the electrocatalytic membrane has a water permeability area of ​​12 × 2 mm, and the filtered water flux is 83.33 L / (m²). 2 Under the condition that the electrocatalytic membrane reduces bromate at a working current density of 2 mA / cm², it filters a solution containing 10 mmol / L sodium sulfate and 1 mg·L⁻¹. -1(with BrO3) - For sodium bromate solutions, the hydraulic retention times were 24, 30, 40, 60, and 120 min, with corresponding membrane fluxes of 208.33, 166.67, 125.00, 83.33, and 41.67 L / (m²). 2 When h), the experimental results are shown in Figure 7 As shown in the figure, BrO3 - The removal rate can reach over 95%.

[0058] Application Example 2:

[0059] Using the electrocatalytic filter membrane prepared in Example 1 as the cathode and a platinum mesh as the anode, the electrocatalytic membrane had a water permeability area of ​​12 × 12 mm, and the filtered water flux was 83.33 L / (m²). 2 The working current density for the electrocatalytic reduction of bromate via the filter membrane is 2 mA / cm² (h). 2 Filtering under conditions containing 10 mmol / L sodium sulfate and 1 mg·L⁻¹ -1 (with BrO3) - (Calculate) Sodium bromate solution, experimental results are shown in […]. Figure 8 As shown in the figure, during the 120 h operation, the removal rate of BrO3- and the corresponding energy consumption remained stable at 95.41 ± 2.81% and 0.75 ± 0.11 kWh / g BrO3, respectively. - .

[0060] Application Example 3:

[0061] Using the electrocatalytic filter membrane prepared in Example 1 as the cathode and a platinum sheet as the anode, the electrocatalytic membrane has a water permeability area of ​​12 × 12 mm, and the filtered water flux is 83.33 L / (m²). 2 The working current density for the electrocatalytic reduction of bromate via the filter membrane is 2 mA / cm² (h). 2 Filtration was performed under the specified conditions. The difference from Application Example 2 is that Application Example 3 used three electrolytes. The first electrolyte contained 10 mmol / L sodium sulfate and 1 mg·L⁻¹ sodium sulfate. -1 (with BrO3) - The first electrolyte is a sodium bromate solution; the second electrolyte is a solution containing 10 mmol / L sodium sulfate, 10 mmol / L sodium chloride, and 1 mg·L⁻¹ sodium chloride. -1 (with BrO3) - The first electrolyte is a sodium bromate solution; the second electrolyte is a solution containing 10 mmol / L sodium sulfate, 10 mmol / L sodium bicarbonate, and 1 mg·L⁻¹ sodium bicarbonate. -1 (with BrO3) - (Calculation) A solution of sodium bromate. Experimental results are shown in... Figure 9As shown in the figure, the presence of chloride ions and bicarbonate ions affects the BrO3 content. - The removal has almost no impact.

[0062] Example 2: Figures 10 to 12 As shown in Comparative Example 1, another embodiment of the present invention is: an electrocatalytic filter membrane for removing bromate from water, which is prepared by the above-described preparation method. The electrocatalytic filter membrane includes carbon nanotube sponge, aminophthalocyanine copper, binder, organic solvent, and DMF solvent. The binder is Nafion 117 solution with a concentration of 5 wt%.

[0063] The ratio of aminophthalocyanine copper to binder is 100~200 g / L by mass / volume. The amount of DMF solvent used is 9 mL-11 mL to meet the requirements of ink preparation. The purity of aminophthalocyanine copper needs to be ≥95%. The organic solvent is N,N-dimethylformamide with a purity of ≥99.8%.

[0064] An apparatus for preparing an electrocatalytic filter membrane for removing bromate from water is disclosed. This apparatus is used to prepare the aforementioned electrocatalytic filter membrane. The membrane comprises a lower housing 1 and an upper housing 2. A pair of outlet pipes 5 are connected to the bottom of the lower housing 1, and an inlet pipe 4 is connected to the top of the upper housing 2. A placement groove 3 is provided at the top of the upper housing 2. A hollow block 6 is fixedly connected to the bottom surface of the inner wall of the lower housing 1. A rotating shaft 8 is rotatably connected to the top of the hollow block 6. A stirring blade 9 is fixedly connected to the outer wall of the rotating shaft 8. A motor 7 for driving the rotating shaft 8 is installed inside the hollow block 6. This application describes the process of injecting DMF solvent from the inlet pipe 4 into… The ink-soaked sponge is placed in the upper shell 2, and then the liquid fills the lower shell 1 and the upper shell 2. Then, the ink-soaked sponge is placed into the upper shell 2 from the placement tank 3 using tweezers. At this time, the sponge is soaked in DMF solvent. Then, the motor 7 is started, which drives the stirring blade 9 to rotate. At this time, the DMF solvent is stirred to wash the sponge. The flowing DMF solvent can improve the washing effect of the sponge. After the first washing is completed, the DMF solvent is discharged from the outlet pipe 5, and new DMF solvent is injected into the upper shell 2 from the inlet pipe 4 to continue washing the sponge. Thus, the sponge is repeatedly washed.

[0065] Application of an electrocatalytic filter membrane for removing bromate from water, wherein the electrocatalytic filter membrane is used to remove bromate from groundwater.

[0066] The lower housing 1 has a sliding groove 10, and the upper housing 2 is disposed within the sliding groove 10. A pair of connecting plates 13 are fixedly connected to the inner wall of the upper housing 2. A first magnetic block 14 is fixedly connected to the bottom surface of the connecting plates 13. A second magnetic block 15, which repels the first magnetic block 14, is fixedly connected to the top surface of the stirring blade 9. A set of return springs is fixedly connected between the bottom surface of the upper housing 2 and the bottom surface of the inner wall of the sliding groove 10. A clamping assembly for clamping the sponge is provided inside the upper housing 2. This application can use the clamping assembly to clamp the sponge, and then the stirring blade... 9. During rotation, the second magnetic block 15 will pass by the first magnetic block 14. At this time, the upper housing 2 will move upward due to the repulsive force between the first magnetic block 14 and the second magnetic block 15. After the second magnetic block 15 passes the first magnetic block 14, the reset spring will pull the upper housing 2 downward to reset. In this way, the second magnetic block 15 continues to pass by the first magnetic block 14, which can make the upper housing 2 shake. During the shaking of the upper housing 2, the sponge held by the clamping component will also shake synchronously, so that the sponge can shake in the DMF solvent, thereby further improving the cleaning effect on the sponge.

[0067] The bottom surface of the upper housing 2 is provided with a connecting groove 11 that communicates with the sliding groove 10. The inner wall of the upper housing 2 is provided with multiple sets of circular holes 12 that communicate with the connecting groove 11. The upper housing 2 and the inner wall of the sliding groove 10 are sealed and slidably connected. When the DMF solvent in this application is injected into the upper housing 2, the DMF solvent will enter the connecting groove 11 and the sliding groove 10 through the circular holes 12. Then, when the upper housing 2 moves, the upper housing 2 will push the liquid in the connecting groove 11 and the sliding groove 10, so that the liquid can be sprayed out from the circular holes 12. At this time, the liquid can be sprayed onto the sponge to impact and clean the sponge, which greatly improves the cleaning effect of the sponge.

[0068] The clamping assembly includes a pair of slide rods 16 slidably connected to the side wall of the upper housing 2. A rectangular plate 18 is fixedly connected to the top surface of the inner wall of the upper housing 2. The slide rods 16 pass through the rectangular plate 18. A connecting ring 17 is fixedly connected to the surface of the slide rods 16. A drive spring 21 is fixedly connected between the connecting ring 17 and the rectangular plate 18. A flexible plate 19 is fixedly connected to the side of the slide rods 16 near the placement groove 3. Multiple sets of protrusions 20 are located on the side of the flexible plate 19 away from the slide rods 16. When the sponge is placed inside the upper housing 2, the slide rods 16 can be pulled to move the pair of flexible plates 19 away from each other. Then, tweezers can be used to place the sponge between the pair of flexible plates 19. After that, the slide rods 16 are released, so that the drive spring 21 pushes the flexible plate 19 to clamp the sponge. The protrusions 20 can create a gap between the flexible plate 19 and the sponge to facilitate washing the sponge with DMF solvent.

[0069] Working principle: DMF solvent is injected into the upper housing 2 through the inlet pipe 4, and the liquid fills the lower housing 1 and the upper housing 2. Then, using tweezers, the ink-soaked sponge is placed into the upper housing 2 from the placement tank 3. The DMF solvent then soaks the sponge. Next, the motor 7 is started, causing the stirring blade 9 to rotate. This agitates the DMF solvent, washing the sponge. The flowing DMF solvent improves the washing effect. After the first wash, the DMF solvent is discharged through the outlet pipe 5, and new DMF solvent is injected into the upper housing 2 through the inlet pipe 4 to continue washing the sponge, thus achieving the desired effect. The sponge is repeatedly washed; this application can use a clamping assembly to clamp the sponge, and when the stirring blade 9 rotates, the second magnetic block 15 will pass the first magnetic block 14. At this time, the upper housing 2 will move upward due to the repulsive force between the first magnetic block 14 and the second magnetic block 15. After the second magnetic block 15 passes the first magnetic block 14, the reset spring will pull the upper housing 2 downward to reset. In this way, the second magnetic block 15 continues to pass the first magnetic block 14, which can make the upper housing 2 shake. During the shaking of the upper housing 2, the sponge clamped by the clamping assembly will also shake synchronously, so that the sponge can shake in the DMF solvent, thereby further improving the cleaning effect of the sponge.

[0070] When the DMF solvent in this application is injected into the upper housing 2, it enters the connecting groove 11 and the sliding groove 10 through the round hole 12. When the upper housing 2 moves, it pushes the liquid in the connecting groove 11 and the sliding groove 10, causing the liquid to spray out from the round hole 12. At this time, the liquid can be sprayed onto the sponge to impact and clean it, greatly improving the cleaning effect. When the sponge is placed in the upper housing 2, the sliding rod 16 can be pulled to move the pair of flexible plates 19 away from each other. Then, tweezers can be used to place the sponge between the pair of flexible plates 19. After that, the sliding rod 16 is released, causing the drive spring 21 to push the flexible plates 19, allowing the flexible plates 19 to clamp the sponge. The protrusion 20 allows there to be a gap between the flexible plates 19 and the sponge, so that the DMF solvent can wash the sponge.

[0071] The terms "front," "back," "left," "right," "top," and "bottom" all refer to the figures in the accompanying drawings. Figure 1 Based on the perspective of the observer, the side of the device facing the observer is defined as the front, the left side of the observer is defined as the left, and so on.

[0072] In the description of this invention, it should be understood that the terms "center", "longitudinal", "lateral", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limiting the scope of protection of this invention.

[0073] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for the preparation of an electrocatalytic filter membrane for the removal of bromate from water; characterized in that: The method comprises the following steps: S1: cutting or selecting carbon nanotube sponge as a substrate with a size of 20*20*1mm, and preparing amino phthalocyanine copper, adhesive, and organic solvent N,N-dimethylformamide; S2: mixing the amino phthalocyanine copper powder with the Nafion 117 solution in the DMF solvent, mixing at room temperature using an ultrasonic device to form a uniform conductive ink, and fully immersing the prepared carbon nanotube sponge in the conductive ink for 8-8.5H to ensure that the sponge is fully in contact with the ink; S3: taking out the soaked sponge from the ink, repeatedly washing it in a cleaner using pure DMF solvent to remove excess ink and unloaded residues, and drying the washed sponge in a vacuum drying box under controlled temperature and time to finally obtain an amino phthalocyanine copper nanosponge; The cleaner in S3 further comprises the following steps during use: A1: by injecting DMF solvent into the upper shell (2) from the liquid inlet pipe (4), filling the DMF solvent in the lower shell (1) and the upper shell (2), placing the sponge between a pair of flexible plates (19) using tweezers, and driving the flexible plates (19) to clamp the sponge by means of the driving spring (21); A2: starting the motor (7) to drive the stirring blade (9) to rotate, at this time the DMF solvent is stirred to wash the sponge, and at the same time the upper shell (2) is shaken by means of the first magnetic block (14) and the second magnetic block (15), so that the DMF solvent can be sprayed from the round hole (12) onto the sponge; A3: after the first washing is completed, the DMF solvent is discharged from the liquid outlet pipe (5), new DMF solvent is injected into the upper shell (2) from the liquid inlet pipe (4) again, and the sponge is washed again to repeatedly wash the sponge.

2. An electrocatalytic filter for removing bromate from water, which is prepared by the production method described in claim 1, characterized in that: The electro-catalytic filter membrane comprises carbon nanotube sponge, amino phthalocyanine copper, adhesive, organic solvent, and DMF solvent, and the adhesive is a Nafion 117 solution with a concentration of 5wt%.

3. The electrocatalytic filter membrane for removing bromate from water according to claim 2, characterized by: The ratio of the amino phthalocyanine copper to the adhesive is 100-200 g / L in mass-volume ratio, the amount of the DMF solvent is 9 mL-11 mL to meet the requirements of ink preparation, the purity of the amino phthalocyanine copper is ≥95%, and the organic solvent is N,N-dimethylformamide with a purity of ≥99.8%.

4. An apparatus for preparing an electrocatalytic filter membrane for removing bromate from water, which is used for preparing the electrocatalytic filter membrane described in claim 3, characterized by: The cleaner comprises a lower shell (1) and an upper shell (2), the bottom end of the lower shell (1) is connected with a pair of liquid outlet pipes (5), the top end of the upper shell (2) is connected with a liquid inlet pipe (4), the top end of the upper shell (2) is provided with a placing groove (3), the inner wall bottom surface of the lower shell (1) is fixedly connected with a hollow block (6), the top end of the hollow block (6) is rotatably connected with a rotating shaft (8), the outer side wall of the rotating shaft (8) is fixedly connected with a stirring blade (9), and the hollow block (6) is provided with a motor (7) for driving the rotating shaft (8) to rotate.

5. The apparatus for preparing an electrocatalytic filter membrane for removing bromate from water according to claim 4, characterized in that: The lower shell (1) is provided with a sliding groove (10), the upper shell (2) is arranged in the sliding groove (10), the inner wall of the upper shell (2) is fixedly connected with a pair of connecting plates (13), the bottom surface of the connecting plate (13) is fixedly connected with a first magnetic block (14), the top surface of the stirring blade (9) is fixedly connected with a second magnetic block (15) repelling the first magnetic block (14), a group of return springs are fixedly connected between the bottom surface of the upper shell (2) and the inner wall bottom surface of the sliding groove (10), and the upper shell (2) is provided with a clamping assembly for clamping the sponge.

6. The apparatus for preparing an electrocatalytic filter membrane for removing bromate from water according to claim 5, characterized in that: The bottom surface of the upper shell (2) is provided with a connecting groove (11) in communication with the sliding groove (10), and the inner wall of the upper shell (2) is provided with a plurality of circular holes (12) in communication with the connecting groove (11).

7. The apparatus for preparing an electrocatalytic filter membrane for removing bromate from water according to claim 6, characterized in that: The clamping assembly comprises a pair of sliding rods (16) slidably connected with the side wall of the upper shell (2), the inner wall top surface of the upper shell (2) is fixedly connected with a rectangular plate (18), the sliding rod (16) penetrates through the rectangular plate (18), the surface of the sliding rod (16) is fixedly connected with a connecting ring (17), the connecting ring (17) and the rectangular plate (18) are fixedly connected with a head driving spring (21), one side of the sliding rod (16) close to the placing groove (3) is fixedly connected with a flexible plate (19), and a plurality of convex blocks (20) are arranged on the side of the flexible plate (19) away from the sliding rod (16).

8. Use of the electrocatalytic filter membrane for removing bromate from water, according to any one of claims 2-3, characterized in that: The electro-catalytic filter membrane is applied to remove bromate in underground water.

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