Cyclic regeneration method and device for acid waste etching liquid

Abstract

The invention relates to the technical field of waste etching liquid treatment, and discloses a cyclic regeneration method and device for waste acidic etching liquid. The method comprises the following steps that cyclic regeneration of etching liquid is achieved through an ionic membrane electrolysis process route, copper ions are effectively converted into metal copper, the etching liquid in an etching production line circularly enters an electrolytic bath, the copper ions in the etching liquid are reduced into the metal copper under the action of current, and the copper ions in the etching liquid are reduced into the metal copper. The chlorine gas which is a byproduct of electrolysis is reused in the production line as an oxidizing agent, so that the ORP (oxidation reduction potential) of the etching liquid is improved, the addition amount of the oxidizing agent of the etching line is effectively reduced, and the tail water after electrolysis is added into the mother liquor of the etching production line under the control of the specific gravity controller, so that the purpose of effectively adjusting the specific gravity of the etching mother liquor is achieved; according to the process, on the basis of electrolytic copper extraction, an electrolytic by-product (chlorine) is effectively utilized, so that the purpose of recycling the waste etching liquid is achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of etching waste liquid treatment, and in particular relates to a recycling method and device for acid waste etching liquid. Background Art

[0002] Etching liquid is a raw material for copperplate engraving. It is a liquid that is engraved by corroding the characteristics of the material. Theoretically, any reagent that can oxidize copper to generate soluble copper salts can be used to etch copper-clad boards, but the damage to the anti-corrosion layer, etching speed, etching coefficient, copper dissolving capacity, solution regeneration and copper recovery, environmental protection and economic effects must be weighed. Etching waste liquid is generated on the etching production line. These waste liquids require a large amount of hydrochloric acid oxidant when they are recycled and regenerated. When the wastewater treatment pool that treats the wastewater generated during the recycling process is in use, once the MBR membrane fibers in the biological treatment pool are broken, the sewage will enter the treatment unit composed of the membrane fibers and pollute the entire membrane fiber treatment unit.

[0003] Therefore, it is necessary to invent a recycling method and device for acid waste etching solution to solve the above problems. Summary of the invention

[0004] In view of the above problems, the present invention provides a method and device for recycling waste acid etching liquid to solve the problems raised in the above background technology.

[0005] To achieve the above object, the present invention provides the following technical solutions: A recycling device for waste acid etching liquid comprises an etching production line, wherein one side of the etching production line is connected to a waste liquid collection barrel, the discharge end of the waste liquid collection barrel is connected to an electrolytic treatment tank, one side of the electrolytic treatment tank is connected to a regeneration collection barrel, the discharge end of the regeneration collection barrel is connected to a multi-stage absorption tower 1, the discharge end of the multi-stage absorption tower 1 is connected to a reuse liquid collection barrel, the discharge end of the reuse liquid collection barrel is connected to an addition system, the addition system is connected to the etching production line, one side of the multi-stage absorption tower 1 is connected to a multi-stage absorption tower 2, one side of the multi-stage absorption tower 2 is connected to a collection box, one side of the multi-stage absorption tower 2 is connected to an exhaust gas treatment device, one side of the exhaust gas treatment device is connected to a wastewater treatment tank, one side of the etching production line is connected to a dissolving absorption cylinder, the lower part of one side of the etching production line is connected to the top of the dissolving absorption cylinder through a connecting pipe, one side of the electrolytic treatment tank is respectively connected to the multi-stage absorption tower 1 and the dissolving absorption cylinder through two branch pipes, the top of the dissolving absorption cylinder is connected to the multi-stage absorption tower 1, and an ORP control system is arranged inside the etching production line.

[0006] Furthermore, the wastewater treatment tank comprises a tank body, wherein a pretreatment tank, a chemical treatment tank, a biological treatment tank and a secondary treatment tank are sequentially arranged inside the tank body, a bracket is arranged inside the biological treatment tank, a channel is arranged inside the bracket, pipes connected to the channel are arranged above and below the bracket, a cover plate is fixedly connected to a side of the pipe close to the center of the bracket, a plurality of groups of sliding openings are equidistantly arranged on the top of the cover plate, a sliding sleeve is slidably installed in the sliding opening, a membrane wire is arranged between the upper and lower opposite sliding sleeves, the sliding sleeve fixing sleeve is arranged on the outside of the membrane wire, a telescopic sleeve is arranged on the outside of the membrane wire, the other side of the telescopic sleeve is fixedly connected to the cover plate, one end of the sliding sleeve extends to the inside of the pipe, a plug assembly is arranged on the outside of the sliding sleeve for closing the end of the sliding sleeve when the membrane wire breaks, a pump body is arranged on the top of the tank body, a water pumping end of the pump body is connected to the internal channel of the bracket, and a drainage end of the pump body is located above the secondary treatment tank.

[0007] Furthermore, the plug assembly includes a ring plate fixedly connected to one end of the sleeve located inside the pipe, the ring plate is fixedly connected to the cover plate via a telescopic tube, the ring plate is fixedly connected to the cover plate via a spring, the telescopic tube is located outside the spring, the end of the sleeve located inside the pipe is provided with a bell mouth, and the interior of the pipe is provided with a plunger assembly for sealing the bell mouth.

[0008] Furthermore, the plunger assembly includes a plunger fixedly mounted on the inner wall of the pipe corresponding to the bell mouth, the end of the plunger close to the bell mouth is in a pointed cone shape, the outer side of the plunger is provided with a fitting surface matching the bell mouth, and the outside of the plunger is provided with a wrapping assembly for wrapping the fitting surface.

[0009] Furthermore, the wrapping assembly includes a cover shell symmetrically sleeved on the outside of the plunger, the interior of the cover shell is provided with a conical groove that cooperates with the conical end of the plunger, the exterior of the cover shell is provided with a fixing assembly for fixing it to the surface of the plunger, and the bottom of the ring plate is symmetrically fixed with a push rod corresponding to the top of the cover shell.

[0010] Furthermore, the fixing assembly includes an iron ring, a ring groove is formed on the outside of the plunger, the iron ring is fixedly sleeved in the ring groove, and a magnet matching the iron ring is fixedly connected to the lower part of the cover shell.

[0011] Furthermore, the multi-stage absorption tower 1 and the multi-stage absorption tower 2 are both provided with spraying equipment.

[0012] The present invention also provides a method for recycling etching solution using the recycling and regeneration device of the acidic waste etching solution as described above, comprising the following steps: S1. When in use, the waste liquid generated by the etching production line enters the waste liquid collection barrel for collection, and then is introduced into the electrolytic treatment cell to react. The cathode reaction formula is: CU2 ++2e=CU 0 , the reaction formula in the anode area is: 2CL - -2e=CL2, copper is generated in this process; S2, the liquid after the reaction enters the regeneration collection bucket for collection, and then is introduced into the multi-stage absorption tower one, the chlorine gas generated during the reaction is introduced into the multi-stage absorption tower one, and the chlorine gas is combined with the liquid by spraying for preparation, and the prepared liquid enters the reuse liquid collection bucket for collection, and then is added to the etching production line through the adding system to achieve the regeneration of the etching liquid; S3, the chlorine gas that has not been completely absorbed by the multi-stage absorption tower 1 enters the multi-stage absorption tower 2 for treatment, and then generates bleaching water or molten iron and collects it in the collection box. Part of the chlorine gas in the process of treatment in the multi-stage absorption tower 2 enters the tail gas treatment equipment for treatment and then discharge, and the generated wastewater enters the wastewater treatment tank for treatment and then discharge; S4. The ORP control system monitors the ORP value in the etching production line. When it is lower than the set ORP value, part of the chlorine generated in the electrolysis process is introduced into the dissolution absorption cylinder, and part of the etching liquid in the etching production line is introduced into the dissolution absorption cylinder. The chlorine generated by electrolysis is dissolved into the etching liquid by spraying to adjust the ORP value of the etching liquid. The adjusted etching liquid is then introduced back into the etching production line to adjust the ORP value of the internal etching liquid. The excess chlorine in the dissolution absorption cylinder enters the multi-stage absorption tower 1 to help with the allocation.

[0013] Technical effects and advantages of the present invention: 1. When the present invention is used, the etching solution is recycled and regenerated and copper ions are effectively converted into metallic copper through the process route of ion membrane electrolysis. The etching solution in the etching production line is circulated into the electrolytic cell. Under the action of the electric current, the copper ions in the etching solution are reduced to metallic copper, and the chlorine gas produced as a by-product of electrolysis is recycled to the production line as an oxidant, so that the ORP of the etching solution is improved, thereby effectively reducing the amount of oxidant added to the etching line, and the tail water after electrolysis is added to the mother liquor of the etching production line under the control of the specific gravity controller, thereby achieving the purpose of effectively adjusting the specific gravity of the etching mother liquor. On the basis of electrolytic copper extraction, this process effectively utilizes the electrolysis by-product (chlorine gas), thereby achieving the purpose of recycling the waste etching solution; 2. When the wastewater treatment pool of the present invention is in use, when the membrane filaments are broken, the ends of the membrane filaments can be sealed, thereby preventing wastewater from contaminating the treatment unit composed of the entire membrane filaments. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 A schematic structural diagram of a recycling and regeneration device for waste acid etching liquid according to an embodiment of the present invention is shown; Figure 2 A schematic diagram showing the structure of a wastewater treatment pool according to an embodiment of the present invention is shown; Figure 3 A schematic diagram showing the structure of a stent and a membrane filament combination according to an embodiment of the present invention is shown; Figure 4 A schematic cross-sectional view of a stent and a partial membrane filament assembly according to an embodiment of the present invention is shown; Figure 5 The embodiment of the present invention is shown Figure 4 The enlarged structural diagram at A in the middle; Figure 6 The embodiment of the present invention is shown Figure 5 The enlarged structural diagram at B in the middle; Figure 7 A schematic structural diagram of a plunger assembly according to an embodiment of the present invention is shown; In the figure: 1. Etching production line; 2. Waste liquid collection barrel; 3. Electrolytic treatment tank; 4. Regeneration collection barrel; 5. Multi-stage absorption tower one; 6. Recycled liquid collection barrel; 7. Addition system; 8. Multi-stage absorption tower two; 9. Collection box; 10. Tail gas treatment equipment; 11. Wastewater treatment tank; 12. Dissolution absorption cylinder; 13. Tank body; 14. Pretreatment tank; 15. Chemical treatment tank; 16. Biological treatment tank; 17. Bracket; 18. Pipeline; 19. Cover plate; 20. Membrane wire; 21. Sliding sleeve; 22. Telescopic sleeve; 23. Ring plate; 24. Spring; 25. Telescopic tube; 26. Bell mouth; 27. Plunger; 28. Cover shell; 29. ​​Magnet; 30. Iron ring; 31. Push rod; 32. Fitting surface; 33. Pump body; 34. Secondary treatment tank. DETAILED DESCRIPTION

[0015] In order to make the purpose, technical solution and advantages of the embodiments of the present invention more clear, the technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments.

[0016] The present invention provides a recycling device for waste acid etching liquid, such as Figures 1 to 7As shown, it includes an etching production line 1, one side of the etching production line 1 is connected to a waste liquid collection barrel 2, the discharge end of the waste liquid collection barrel 2 is connected to an electrolytic treatment cell 3, one side of the electrolytic treatment cell 3 is connected to a regeneration collection barrel 4, the discharge end of the regeneration collection barrel 4 is connected to a multi-stage absorption tower 5, the discharge end of the multi-stage absorption tower 5 is connected to a reuse liquid collection barrel 6, the discharge end of the reuse liquid collection barrel 6 is connected to an addition system 7, the addition system 7 is connected to the etching production line 1, the addition system 7 is a specific gravity controller, one side of the multi-stage absorption tower 5 is connected to a multi-stage absorption tower 8, A collecting box 9 is connected to one side of the second-stage absorption tower 8, a tail gas treatment device 10 is connected to one side of the multi-stage absorption tower 8, a wastewater treatment tank 11 is connected to one side of the tail gas treatment device 10, a dissolving absorption cylinder 12 is connected to one side of the etching production line 1, a lower part of one side of the etching production line 1 is connected to the top of the dissolving absorption cylinder 12 through a connecting pipe, one side of the electrolytic treatment pool 3 is connected to the multi-stage absorption tower 1 5 and the dissolving absorption cylinder 12 through two branch pipes, the top of the dissolving absorption cylinder 12 is connected to the multi-stage absorption tower 1 5, and an ORP control system is provided inside the etching production line 1.

[0017] When in use, the waste liquid generated by the etching production line 1 enters the waste liquid collection barrel 2 for collection, and then is introduced into the electrolytic treatment cell 3 to react. The cathode reaction formula is: CU2 + +2e=CU 0 , the reaction formula in the anode area is: 2CL - -2e=CL2, high purity copper is generated in this process, the liquid after the reaction enters the regeneration collection barrel 4 for collection, and then is introduced into the multi-stage absorption tower 1 5, the chlorine generated during the reaction is introduced into the multi-stage absorption tower 1 5, the chlorine gas and the liquid are combined by spraying for preparation, the prepared liquid enters the reuse liquid collection barrel 6 for collection, and then is added to the etching production line 1 through the adding system 7 to achieve the regeneration of the etching liquid, the chlorine gas that has not been completely absorbed by the multi-stage absorption tower 1 5 enters the multi-stage absorption tower 2 8 for treatment, and then the bleaching water or molten iron is generated and collected in the collection box 9, and part of the chlorine gas in the process of treatment in the multi-stage absorption tower 2 8 enters the tail gas treatment equipment 10 After treatment, the wastewater is discharged after treatment in the wastewater treatment tank 11. The ORP control system monitors the ORP value in the etching production line 1. When it is lower than the set OPR value, part of the chlorine generated in the electrolysis process is introduced into the dissolution absorption cylinder 12, and part of the etching liquid in the etching production line 1 is introduced into the dissolution absorption cylinder 12. The chlorine generated by electrolysis is melted into the etching liquid by spraying to adjust the ORP value of the etching liquid. Then, the adjusted etching liquid is introduced back into the etching production line 1 to adjust the ORP value of the internal etching liquid. The excess chlorine in the dissolution absorption cylinder 12 enters the multi-stage absorption tower 5 to help with the deployment; When the entire device is in use, the etching solution is recycled and regenerated and copper ions are effectively converted into metallic copper through the process route of ion membrane electrolysis. The etching solution in the etching production line 1 is circulated into the electrolytic cell. Under the action of the electric current, the copper ions in the etching solution are reduced to metallic copper, and the chlorine gas produced as a byproduct of electrolysis is reused in the production line as an oxidant, so that the ORP of the etching solution is improved, thereby effectively reducing the amount of oxidant added to the etching line. The tail water after electrolysis is added to the mother liquor of the etching production line 1 under the control of the specific gravity controller, thereby effectively adjusting the specific gravity of the etching mother liquor. This process effectively utilizes the chlorine gas produced as a byproduct of electrolysis on the basis of copper extraction by electrolysis, thereby achieving the purpose of recycling waste etching solution.

[0018] like Figures 2 to 7 As shown, the wastewater treatment tank 11 includes a tank body 13, and a pretreatment tank 14, a chemical treatment tank 15, a biological treatment tank 16 and a secondary treatment tank 34 are arranged in sequence inside the tank body 13. The pretreatment tank 14, the chemical treatment tank 15, the biological treatment tank 16 and the secondary treatment tank 34 are the pretreatment tank, the chemical treatment tank, the biological treatment tank and the secondary treatment tank in the treatment equipment for treating the wastewater generated by chlorine treatment in the prior art. The specific treatment principle is the prior art and will not be repeated here. A bracket 17 is arranged inside the biological treatment tank 16, and a channel is arranged inside the bracket 17. Pipes 18 connected to the channel are arranged above and below the inside of the bracket 17, and a cover plate 19 is fixedly connected to one side of the pipe 18 close to the center of the bracket 17 A plurality of sliding openings are equidistantly arranged on the top of the cover plate 19, and a sliding sleeve 21 is slidably installed in the sliding opening. A membrane thread 20 is arranged between the upper and lower opposite sliding sleeves 21. The sliding sleeve 21 is fixedly sleeved on the outside of the membrane thread 20, and a telescopic sleeve 22 is provided on the outer fixed sleeve of the membrane thread 20. The other side of the telescopic sleeve 22 is fixedly connected to the cover plate 19. One end of the sliding sleeve 21 extends to the inside of the pipeline 18, and a plug assembly is provided on the outside of the sliding sleeve 21 for closing the end of the sliding sleeve 21 when the membrane thread 20 is broken. A pump body 33 is arranged on the top of the pool body 13, and the water pumping end of the pump body 33 is connected to the internal channel of the bracket 17, and the drainage end of the pump body 33 is located above the secondary treatment pool 34. The membrane thread 20 is an MBR membrane thread, and its filter holes are distributed between the upper and lower telescopic sleeves 22.

[0019] During use, wastewater enters the tank body 13 and is treated in the pretreatment tank 14, the chemical treatment tank 15, the biological treatment tank 16 and the secondary treatment tank 34 before being discharged in compliance with the standards. When the wastewater is treated in the biological treatment tank 16, the pump body 33 works at this time, so that the wastewater passes through the filter holes of the membrane filament 20 and enters the membrane filament 20, and then enters the channel, and is finally pumped out by the pump body 33 and discharged into the secondary treatment tank 34. With long-term use, the membrane filament 20 is cut off by large impurity particles in the wastewater. At this time, the plug assembly seals the end of the sleeve 21, and wastewater will not enter the broken membrane filament 20, thereby preventing wastewater from contaminating the entire treatment unit composed of the membrane filament 20.

[0020] like Figure 5 and Figure 6 As shown, the plug assembly includes a ring plate 23 fixedly connected to one end of the sleeve 21 located inside the pipe 18, the ring plate 23 is fixedly connected to the cover plate 19 through a telescopic tube 25, the ring plate 23 is fixedly connected to the cover plate 19 through a spring 24, the telescopic tube 25 is located outside the spring 24, a bell mouth 26 is provided at one end of the sleeve 21 located inside the pipe 18, and a plunger assembly for sealing the bell mouth 26 is provided inside the pipe 18.

[0021] When in use, the membrane filament 20 can pull the sliding sleeve 21 and the ring plate 23 to move with it when it swings, so that the spring 24 is compressed. When the swing amplitude becomes smaller, the spring 24 brings the ring plate 23 and the sliding sleeve 21 to reset. When the ring plate 23 is reset, the spring 24 is still in a compressed state. During the whole process, the spring 24 adaptively compresses and stretches to adapt to the swing of the membrane filament 20. When the membrane filament 20 breaks, the compressed spring 24 releases the force to move the ring plate 23, the sliding sleeve 21, and the membrane filament 20, so that it is close to the plunger assembly, so that the bell mouth 26 is closed by the plunger assembly, and the end of the membrane filament 20 is blocked.

[0022] like Figures 5 to 7 As shown, the plunger assembly includes a plunger 27 fixedly mounted on the inner wall of the pipe 18 and corresponding to the bell-mouth 26. The end of the plunger 27 close to the bell-mouth 26 is in a pointed cone shape. The outer side of the plunger 27 is provided with a fitting surface 32 matching the bell-mouth 26. The outside of the plunger 27 is provided with a wrapping assembly for wrapping the fitting surface 32.

[0023] By wrapping the fitting surface 32 with the wrapping component, foreign particles are prevented from sticking to the fitting surface 32. When the membrane filament 20 breaks, the sleeve 21 moves toward the direction close to the plunger 27. At this time, the wrapping component cancels the wrapping of the fitting surface 32. At this time, the clean fitting surface 32 leaks out, and then the bell-mouth 26 is combined with the fitting surface 32 to seal the sleeve 21, thereby achieving the sealing of the end of the membrane filament 20. Since the fitting surface 32 is clean, it is more tightly combined with the bell-mouth 26, and the sealing effect is better.

[0024] like Figures 5 to 7 As shown, the wrapping assembly includes a cover shell 28 symmetrically sleeved on the outside of the plunger 27, the interior of the cover shell 28 is provided with a conical groove that cooperates with the conical end of the plunger 27, and the exterior of the cover shell 28 is provided with a fixing assembly for fixing it to the surface of the plunger 27, and a push rod 31 corresponding to the top of the cover shell 28 is symmetrically fixedly installed on the bottom of the ring plate 23, and there is a gap between the push rod 31 and the cover shell 28. The size of the gap is sufficient to provide the space range required for the sliding sleeve 21, the ring plate 23, and the push rod 31 to move accordingly when the membrane wire 20 swings. Therefore, when the membrane wire 20 swings, the push rod 31 will not contact the cover shell 28.

[0025] As the membrane filament 20 breaks, the sliding sleeve 21, the ring plate 23, and the push rod 31 move, and the push rod 31 collides with the cover shell 28, squeezing it, so that the fixing assembly cancels the fixation of the cover shell 28, and the cover shell 28 is separated from the fitting surface 32, and then the bell mouth 26 collides with the plunger 27 and the fitting surface 32 to achieve sealing.

[0026] like Figure 6 and Figure 7 As shown, the fixing assembly includes an iron ring 30 , an annular groove is formed on the outside of the plunger 27 , the iron ring 30 is fixedly sleeved in the annular groove, and a magnet 29 matching the iron ring 30 is fixedly connected to the lower part of the cover shell 28 .

[0027] After the push rod 31 contacts the cover shell 28 , it squeezes it, so that the cover shell 28 overcomes the suction force between the magnet 29 and the iron ring 30 to move, and finally the magnet 29 and the iron ring 30 are separated, and the fixation of the cover shell 28 is cancelled.

[0028] like Figure 1 As shown, the multi-stage absorption tower 1 5 and the multi-stage absorption tower 2 8 are both provided with spraying equipment.

[0029] The multi-stage absorption tower 1 5 and the multi-stage absorption tower 2 8 are multi-stage absorption towers in the prior art.

[0030] The present invention also provides a method for recycling etching solution using the recycling and regeneration device of the acid waste etching solution as described above, comprising the following steps: S1, when in use, the waste liquid generated by the etching production line 1 enters the waste liquid collection barrel 2 for collection, and then is introduced into the electrolytic treatment cell 3 to react. The cathode reaction formula is: CU2 + +2e=CU 0 , the reaction formula in the anode area is: 2CL - -2e=CL2, copper is generated in this process; S2, the liquid after the reaction enters the regeneration collection barrel 4 for collection, and then is introduced into the multi-stage absorption tower 5, the chlorine gas generated during the reaction is introduced into the multi-stage absorption tower 5, and the chlorine gas is combined with the liquid by spraying for preparation, and the prepared liquid enters the reuse liquid collection barrel 6 for collection, and then is added to the etching production line 1 through the adding system 7 to achieve the regeneration of the etching liquid; S3, the chlorine gas that has not been completely absorbed by the multi-stage absorption tower 1 5 enters the multi-stage absorption tower 2 8 for treatment, and then generates bleaching water or molten iron and collects it in the collection box 9, and part of the chlorine gas in the process of treatment in the multi-stage absorption tower 2 8 enters the tail gas treatment equipment 10 for treatment and then discharge, and the generated wastewater enters the wastewater treatment tank 11 for treatment and then discharge; S4, the ORP control system monitors the ORP value in the etching production line 1. When it is lower than the set ORP value, part of the chlorine gas generated in the electrolysis process is introduced into the dissolving absorption cylinder 12, and part of the etching liquid in the etching production line 1 is introduced into the dissolving absorption cylinder 12. The chlorine gas generated by electrolysis is dissolved in the etching liquid by spraying to adjust the ORP value of the etching liquid. The adjusted etching liquid is then introduced back into the etching production line 1 to adjust the ORP value of the internal etching liquid. The excess chlorine gas in the dissolving absorption cylinder 12 enters the multi-stage absorption tower 5 to help with the allocation.

[0031] Working principle: When in use, the waste liquid generated by the etching production line 1 enters the waste liquid collection barrel 2 for collection, and then is introduced into the electrolytic treatment cell 3 to react. The cathode reaction formula is: CU2 + +2e=CU 0 , the reaction formula in the anode area is: 2CL - -2e=CL2, copper is generated in this process, the liquid after the reaction enters the regeneration collection barrel 4 for collection, and then is introduced into the multi-stage absorption tower 1 5, the chlorine generated during the reaction is introduced into the multi-stage absorption tower 1 5, the chlorine gas and the liquid are combined by spraying for preparation, the prepared liquid enters the reuse liquid collection barrel 6 for collection, and then is added to the etching production line 1 through the adding system 7 to achieve the regeneration of the etching liquid, the chlorine gas that has not been completely absorbed by the multi-stage absorption tower 1 5 enters the multi-stage absorption tower 2 8 for treatment, and then the bleaching water or molten iron is generated and collected in the collection box 9, and part of the chlorine gas in the process of treatment in the multi-stage absorption tower 2 8 enters the tail gas treatment equipment 10 for treatment. The generated wastewater is discharged after treatment in the wastewater treatment tank 11, and the ORP control system monitors the ORP value in the etching production line 1. When it is lower than the set OPR value, part of the chlorine generated in the electrolysis process is introduced into the dissolving absorption cylinder 12, and part of the etching liquid in the etching production line 1 is introduced into the dissolving absorption cylinder 12. The chlorine generated by electrolysis is melted into the etching liquid by spraying, so that the ORP value of the etching liquid is adjusted, and then the adjusted etching liquid is introduced back into the etching production line 1, so that the ORP value of the internal etching liquid is adjusted, and the excess chlorine in the dissolving absorption cylinder 12 enters the multi-stage absorption tower 5 to help with the deployment; During use, wastewater enters the tank body 13 and is treated in the pretreatment tank 14, the chemical treatment tank 15, the biological treatment tank 16 and the secondary treatment tank 34 before being discharged in compliance with the standards. When the wastewater is treated in the biological treatment tank 16, the pump body 33 works at this time, so that the wastewater passes through the filter holes of the membrane filament 20 and enters the membrane filament 20, and then enters the channel, and is finally pumped out by the pump body 33 and discharged into the secondary treatment tank 34. With long-term use, the membrane filament 20 is cut off by large impurity particles in the wastewater. At this time, the compressed spring 24 releases its force to move the ring plate 23, the sleeve 21 and the membrane filament 20, so that they are close to the plunger 27. The cover shell 28 wraps the plunger 27 to prevent the fitting surface 32 from sticking to the impurity particles. The movement of the ring plate 23, the sliding sleeve 21, and the membrane filament 20 causes the push rod 31 to move accordingly. After the push rod 31 collides with the cover shell 28, it is squeezed so that the cover shell 28 overcomes the suction force between the magnet 29 and the iron ring 30 and moves, and finally the magnet 29 is separated from the iron ring 30, and the fixation of the cover shell 28 is cancelled. The cover shell 28 is separated from the fitting surface 32, and then the bell mouth 26 collides with the plunger 27 and the fitting surface 32 to achieve the plugging of the sliding sleeve 21. Due to the cleanliness of the fitting surface 32, it is more tightly combined with the bell mouth 26 and the sealing effect is better. At this point, the end of the membrane filament 20 is blocked. At this time, wastewater will not enter the broken membrane filament 20, thereby preventing wastewater from polluting the entire treatment unit composed of the membrane filament 20.

[0032] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them.

Claims

1. A recycling device for waste acid etching liquid, comprising an etching production line (1), characterized in that: One side of the etching production line (1) is connected to a waste liquid collection barrel (2), the discharge end of the waste liquid collection barrel (2) is connected to an electrolytic treatment cell (3), one side of the electrolytic treatment cell (3) is connected to a regeneration collection barrel (4), the discharge end of the regeneration collection barrel (4) is connected to a multi-stage absorption tower (5), the discharge end of the multi-stage absorption tower (5) is connected to a reuse liquid collection barrel (6), the discharge end of the reuse liquid collection barrel (6) is connected to an addition system (7), the addition system (7) is connected to the etching production line (1), one side of the multi-stage absorption tower (5) is connected to a multi-stage absorption tower (8), one side of the multi-stage absorption tower (8) is connected to a multi-stage absorption tower (8), and one side of the multi-stage absorption tower (8) is connected to a multi-stage absorption tower (8). A collecting box (9) is connected to one side of the multi-stage absorption tower (2) (8); an exhaust gas treatment device (10) is connected to one side of the exhaust gas treatment device (10); a wastewater treatment tank (11) is connected to one side of the etching production line (1); a dissolving absorption cylinder (12) is connected to one side of the etching production line (1); a lower part of one side of the etching production line (1) is connected to the top of the dissolving absorption cylinder (12) through a connecting pipe; one side of the electrolytic treatment pool (3) is respectively connected to the multi-stage absorption tower (5) and the dissolving absorption cylinder (12) through two branch pipes; the top of the dissolving absorption cylinder (12) is connected to the multi-stage absorption tower (5); and an ORP control system is provided inside the etching production line (1).

2. The recycling and regeneration device for waste acidic etching solution according to claim 1, characterized in that: The wastewater treatment tank (11) comprises a tank body (13), wherein a pretreatment tank (14), a chemical treatment tank (15), a biological treatment tank (16) and a secondary treatment tank (34) are sequentially arranged inside the tank body (13), wherein a bracket (17) is arranged inside the biological treatment tank (16), wherein a channel is arranged inside the bracket (17), wherein pipes (18) communicating with the channel are arranged above and below the bracket (17), wherein a cover plate (19) is fixedly connected to one side of the pipe (18) close to the center of the bracket (17), wherein a plurality of groups of sliding openings are equidistantly arranged on the top of the cover plate (19), wherein a sliding sleeve (21) is slidably installed in the sliding opening, wherein two upper and lower opposite sliding sleeves (21) are arranged on the upper and lower sides of the sliding sleeves (21) A membrane filament (20) is arranged between the sleeves (21); the sliding sleeve (21) is fixedly arranged on the outside of the membrane filament (20); a telescopic sleeve (22) is arranged on the outside of the membrane filament (20); the other side of the telescopic sleeve (22) is fixedly connected to the cover plate (19); one end of the sliding sleeve (21) extends to the inside of the pipeline (18); a plug assembly is arranged on the outside of the sliding sleeve (21) for closing the end of the sliding sleeve (21) when the membrane filament (20) is broken; a pump body (33) is arranged on the top of the pool body (13); a water pumping end of the pump body (33) is connected to the internal channel of the bracket (17); and a water discharge end of the pump body (33) is located above the secondary treatment pool (34).

3. The recycling and regeneration device for waste acidic etching solution according to claim 2, characterized in that: The plug assembly comprises a ring plate (23) fixedly connected to one end of the sliding sleeve (21) located inside the pipe (18); the ring plate (23) is fixedly connected to the cover plate (19) via a telescopic tube (25); the ring plate (23) is fixedly connected to the cover plate (19) via a spring (24); the telescopic tube (25) is located outside the spring (24); a bell mouth (26) is provided at one end of the sliding sleeve (21) located inside the pipe (18); and a plunger assembly for blocking the bell mouth (26) is provided inside the pipe (18).

4. The recycling and regeneration device for waste acid etching solution according to claim 3, characterized in that: The plunger assembly comprises a plunger (27) fixedly mounted on the inner wall of the pipe (18) and corresponding to the bell mouth (26); one end of the plunger (27) close to the bell mouth (26) is in a pointed cone shape; the outer side of the plunger (27) is provided with a fitting surface (32) matching the bell mouth (26); and the outside of the plunger (27) is provided with a wrapping assembly for wrapping the fitting surface (32).

5. The recycling and regeneration device for waste acid etching solution according to claim 4, characterized in that: The wrapping assembly comprises a cover shell (28) symmetrically sleeved on the outside of the plunger (27); the cover shell (28) is provided with a pointed conical groove inside to match the pointed conical end of the plunger (27); the cover shell (28) is provided with a fixing assembly outside to fix it to the surface of the plunger (27); and a push rod (31) corresponding to the top of the cover shell (28) is symmetrically fixedly mounted on the bottom of the ring plate (23).

6. The recycling and regeneration device for waste acidic etching solution according to claim 5, characterized in that: The fixing assembly comprises an iron ring (30), an annular groove is formed on the outside of the plunger (27), the iron ring (30) is fixedly sleeved in the annular groove, and a magnet (29) matching the iron ring (30) is fixedly connected to the lower part of the cover shell (28).

7. The recycling and regeneration device for waste acidic etching liquid according to claim 6, characterized in that: The multi-stage absorption tower 1 (5) and the multi-stage absorption tower 2 (8) are both provided with spraying equipment inside.

8. A method for recycling etching solution using the recycling device for waste acid etching solution as claimed in claim 7, characterized in that: The steps include: S1. When in use, the waste liquid generated by the etching production line (1) enters the waste liquid collection bucket (2) for collection, and then is introduced into the electrolytic treatment cell (3) to react. The cathode reaction formula is: CU2 + +2e=CU 0 , the reaction formula in the anode area is: 2CL - -2e=CL2, copper is generated in this process; S2, the liquid after the reaction enters the regeneration collection barrel (4) for collection, and then is introduced into the multi-stage absorption tower (5), the chlorine gas generated during the reaction is introduced into the multi-stage absorption tower (5), and the chlorine gas is combined with the liquid by spraying for mixing, and the mixed liquid enters the reuse liquid collection barrel (6) for collection, and then is added to the etching production line (1) through the adding system (7) to achieve the regeneration of the etching liquid; S3, the chlorine gas that has not been completely absorbed by the multi-stage absorption tower 1 (5) enters the multi-stage absorption tower 2 (8) for treatment, and then the generated bleaching water or molten iron is collected in the collection box (9), and part of the chlorine gas in the process of being treated in the multi-stage absorption tower 2 (8) enters the tail gas treatment equipment (10) for treatment and then discharged, and the generated wastewater enters the wastewater treatment pool (11) for treatment and then discharged; S4, the ORP control system monitors the ORP value in the etching production line (1). When the ORP value is lower than the set ORP value, part of the chlorine gas generated during the electrolysis process is introduced into the dissolving absorption cylinder (12), and part of the etching liquid in the etching production line (1) is introduced into the dissolving absorption cylinder (12). The chlorine gas generated by the electrolysis is dissolved into the etching liquid by spraying, so that the ORP value of the etching liquid is adjusted. The adjusted etching liquid is then introduced back into the etching production line (1) to adjust the ORP value of the etching liquid inside. The excess chlorine gas in the dissolving absorption cylinder (12) enters the multi-stage absorption tower (5) to help with the mixing.

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