A multi-stage treatment device and method for manganese sulfate wastewater containing benzoquinone

Through multi-stage treatment methods and special equipment, the problem of removing organic matter and heavy metals in manganese sulfate wastewater was solved, the production of high-purity electrolytic manganese was achieved, and the economic benefits and electrolysis efficiency were improved.

CN119874134BActive Publication Date: 2025-09-30WUDI YINENG CHEM CO LTD
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Patent Information

Application Number
CN202510351961.5
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2025-03-24
Publication Date
2025-09-30
Estimated Expiration
2045-03-24

AI Technical Summary

Technical Problem

In the existing technology, organic matter and heavy metals such as benzoquinone and aniline sulfate cannot be effectively removed, resulting in blackening of the cathode plate during electrolysis of manganese sulfate wastewater, inversion caused by heavy metal zinc, and increased pH value, low economic value, and increased power consumption.

Method used

A multi-stage treatment method is adopted, including leaching to remove benzoquinone, neutralization to remove iron and nickel, sulfide to remove zinc and organic matter, static standing and fine filtration, combined with the stirring and sampling mechanism of special equipment to achieve deep purification.

Benefits of technology

Effectively remove organic matter and heavy metals from manganese sulfate wastewater to obtain electrolytic manganese products with a purity of more than 99.8%, increasing it to 99.9%, with good environmental and economic benefits.

✦ Generated by Eureka AI based on patent content.

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Abstract

The present invention relates to the field of wastewater treatment technology, specifically disclosing a multi-stage treatment device and method for manganese sulfate wastewater containing benzoquinone. The device and method include four steps: leaching to remove benzoquinone, neutralization to remove iron and nickel, sulfidation to remove zinc and organic matter, and standing. The device and method also include a first neutralization tank, a second neutralization tank, and a base. The first and second neutralization tanks are both arranged on top of the base. The first neutralization tank is provided with a first stirring mechanism, and the second neutralization tank is provided with an auxiliary sampling mechanism and a second stirring mechanism. The treatment device and method provided in the present invention can deeply purify manganese sulfate wastewater, thereby effectively removing organic matter and heavy metals in the manganese sulfate wastewater. After reaching electrolysis standards, electrolysis can produce an electrolytic manganese product with a purity of more than 99.8%, and various heavy metal indicators are also qualified, providing a basis for upgrading the purity of electrolytic manganese to 99.9%. The device and method have excellent environmental and economic benefits and are conducive to practical industrial applications.
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Description

Technical Field

[0001] The present invention relates to the technical field of wastewater treatment, and in particular to a multi-stage treatment device and method for manganese sulfate wastewater containing benzoquinone. Background Art

[0002] The production of hydroquinone by the aniline redox method generates a large amount of manganese sulfate wastewater, which is generally electrolyzed into metallic manganese in the industry. Traditional purification treatment alone cannot remove organic matter and heavy metals such as benzoquinone and aniline sulfate from the wastewater. Benzoquinone and aniline sulfate can cause the cathode plate to turn black during electrolysis, and heavy metal zinc can cause the solution to melt and increase the pH value during electrolysis. As a result, the output of metallic manganese produced is low, power consumption is increased, and economic value and market recognition are very low.

[0003] Based on the above problems and needs, the present invention provides a multi-stage treatment device and method for manganese sulfate wastewater containing benzoquinone. By deeply purifying the manganese sulfate wastewater, organic matter and heavy metals in the wastewater can be effectively removed. After reaching the electrolysis standard, electrolytic manganese products with a purity of more than 99.8% can be obtained through electrolysis. Various heavy metal indicators are also qualified, which provides a basis for upgrading the purity of electrolytic manganese to 99.9%. Summary of the Invention

[0004] The purpose of the present invention is to solve the shortcomings of the prior art and to provide a multi-stage treatment device and method for manganese sulfate wastewater containing benzoquinone.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] A multi-stage treatment method for manganese sulfate wastewater containing benzoquinone, the treatment method comprising the following steps:

[0007] Step 1: Leaching and removing benzoquinone, the manganese sulfate wastewater and clean water are put into the first neutralization tank at a ratio of 3:1, and then the mixed manganese sulfate wastewater is heated and stirred. After the manganese sulfate wastewater is heated to 90°C, the benzoquinone in the manganese sulfate wastewater evaporates with the steam. Then the manganese sulfate wastewater is closed and stirred and allowed to stand for 6 hours, and the manganese sulfate wastewater is subjected to the first filter press;

[0008] Step 2: Neutralization to remove iron and nickel. The manganese sulfate wastewater after the first filter press in step 1 is introduced into a second neutralization barrel for aeration. Then, ammonia water, sodium thiamethoxam, industrial activated carbon and polyacrylamide are added to the second neutralization barrel in sequence. After mixing and stirring, the mixture is allowed to stand for 5 hours and then the second filter press is performed.

[0009] Step 3: Sulfurization to remove zinc and organic matter. The manganese sulfate wastewater after the second filter press in step 2 is introduced into a sulfidation barrel. Sulfuric acid, sodium sulfide, and polyacrylamide are added to the sulfidation barrel in sequence. After mixing and stirring, the mixture is precipitated for 5 hours and then the third filter press is performed.

[0010] Step 4: Standing, hydrogen peroxide is added to the manganese sulfate wastewater after the third filter press in step 3 and the solution is allowed to stand for 24 hours. After the standing, the fourth fine filtration is performed to complete the purification of the manganese sulfate wastewater.

[0011] Optionally, a multi-stage treatment device for manganese sulfate wastewater containing benzoquinone is provided, which is applied to the above-mentioned treatment method. The device includes a first neutralization barrel, a second neutralization barrel and a base. The first neutralization barrel and the second neutralization barrel are both arranged on the top of the base. The top and bottom of the first neutralization barrel are respectively provided with a first water inlet and a first outlet. The top of the first neutralization barrel is also provided with multiple steam outlets. The interior of the first neutralization barrel is provided with a first stirring mechanism for stirring the manganese sulfate wastewater. The top and bottom of the second neutralization barrel are respectively provided with a second water inlet and a second outlet. The interior of the second neutralization barrel is respectively provided with an auxiliary sampling mechanism for facilitating sampling of the manganese sulfate wastewater and a second stirring mechanism.

[0012] Optionally, a mounting plate is installed between the first neutralization barrel and the second neutralization barrel, the water pump is installed on the top of the mounting plate, and the first pipe and the second pipe are installed at the input end and the output end of the water pump respectively, and the first pipe and the second pipe extend to the interior of the first neutralization barrel and the second neutralization barrel respectively at one end away from the water pump.

[0013] Optionally, the first stirring mechanism includes a first motor installed on the top of the first neutralization barrel, the output end of the first motor passes through the first neutralization barrel and is connected to a first rotating shaft, and a plurality of first stirring blades are installed on the outer wall of the first rotating shaft.

[0014] Optionally, the second stirring mechanism includes a second motor installed inside the base, the output end of the second motor passes through the second neutralization barrel and is connected to a second rotating shaft, and a plurality of second stirring blades are installed on the outer wall of the second rotating shaft.

[0015] Optionally, the auxiliary sampling mechanism includes a third motor installed on the top of the second neutralization barrel, the output end of the third motor passes through the second neutralization barrel and is connected to a third rotating shaft, the outer wall of the third rotating shaft is provided with a plurality of limit grooves, and a movable frame is provided inside the second neutralization barrel, and the movable frame slides up and down inside the limit groove through a plurality of limit blocks provided on the inner wall.

[0016] Optionally, two fixed plates are installed on the top of the second neutralization barrel, and the outer walls of the two fixed plates on the side close to each other are provided with sliding grooves, and sliders are installed inside the two sliding grooves, and sliding rods are installed at the bottom ends of the two sliders, and connecting ends are installed at the bottom ends of the two sliding rods, and a circular groove is provided on the top of the movable frame to slide with the two connecting ends.

[0017] Optionally, two fixed seats are installed at the bottom end of the movable frame, and two rotating plates are installed inside the two fixed seats through connecting shafts. The outer walls of both ends of the two connecting shafts are equipped with torsion springs, and the interiors of the two rotating plates are provided with storage grooves. The bottom ends of the two rotating plates are provided with multiple drainage holes connected to the storage grooves.

[0018] Optionally, a plurality of connecting rods are installed on the outer wall of the movable frame, and a circular cleaning brush is commonly installed on one end of the plurality of connecting rods away from the movable frame.

[0019] Optionally, two rectangular grooves are opened inside the movable frame, and a fourth motor is installed inside the two rectangular grooves. Winding wheels are installed at the output ends of the two fourth motors, and connecting ropes are wound on the surfaces of the two winding wheels. The ends of the two connecting ropes away from the winding wheels are connected to the rotating plate close to them.

[0020] The beneficial effects of the present invention are:

[0021] 1. The treatment device and treatment method provided in the present invention can deeply purify manganese sulfate wastewater, thereby effectively removing organic matter and heavy metals in the manganese sulfate wastewater. After reaching the electrolysis standard, electrolytic manganese products with a purity of more than 99.8% can be obtained through electrolysis. Various heavy metal indicators are also qualified, which has the basis for upgrading to electrolytic manganese with a purity of 99.9%. It has good environmental and economic benefits and is conducive to actual industrial application.

[0022] 2. In this invention, when it is necessary to sample and test the wastewater in the second neutralization barrel, the auxiliary sampling mechanism provided inside the second neutralization barrel cooperates with each other, so that after the wastewater enters the storage tank, one of the rotating plates moves to directly below the second water inlet. The staff can insert the bottom end of the sampling test tube into one of the storage tanks through the second water inlet to quickly sample the wastewater collected in the storage tank, thereby avoiding the problem that the wastewater level inside the second neutralization barrel is low and it is inconvenient to manually use a test tube for sampling, thereby improving the staff's sampling efficiency of the wastewater and facilitating rapid testing of the wastewater.

[0023] 3. In the present invention, in the process of mixing and stirring the wastewater and other additives by the second stirring mechanism, a lot of foam will inevitably be produced on the surface of the wastewater. In order to prevent the additives in the foam from being mixed in the wastewater, resulting in a low reaction efficiency with the wastewater, the movable frame is immersed in the wastewater again until the two receiving tanks collect part of the wastewater, and then the movable frame is controlled to move upward to above the wastewater. As the third motor drives the movable frame to rotate, the multiple drainage holes at the bottom of the two rotating plates can sprinkle the wastewater collected in the receiving tank downward, defoaming the foam on the surface of the wastewater, thereby improving the efficiency of the mixing reaction between the additives and the wastewater, and facilitating the purification and removal of harmful substances in the wastewater.

[0024] 4. In the present invention, after the wastewater inside the second neutralization barrel is discharged, in order to facilitate the subsequent use of the second neutralization barrel, the second neutralization barrel needs to be cleaned. At this time, the two sliders can be controlled to move up and down inside the corresponding slide grooves. With the help of the up and down movement of the two slide rods, the movable frame is driven to move up and down synchronously inside the second neutralization barrel, so that the cleaning brush arranged on the outer wall of the movable frame can automatically clean the impurities attached to the inner wall of the second neutralization barrel during the up and down movement, so that the second neutralization barrel can be quickly put into use in the subsequent wastewater purification process, thereby indirectly improving the efficiency of wastewater treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] To facilitate understanding by those skilled in the art, the present invention is further described below with reference to the accompanying drawings.

[0026] Figure 1 This is a schematic diagram of the overall structure of a multi-stage treatment device for manganese sulfate wastewater containing benzoquinone proposed by the present invention;

[0027] Figure 2 for Figure 1 a structural cross-sectional view of the first neutralization barrel and the second neutralization barrel;

[0028] Figure 3 This is a schematic diagram of the structure inside the second neutralization barrel of the present invention;

[0029] Figure 4 Schematic diagram of the structure of the second stirring mechanism in the present invention;

[0030] Figure 5 A schematic structural diagram of one of the fixed plates and the sliding rod in the present invention;

[0031] Figure 6 Schematic diagram of the structure of the movable frame and the third rotating shaft in the present invention;

[0032] Figure 7 It is a structural schematic diagram of the bottom of the movable frame in the present invention;

[0033] Figure 8 This is a schematic structural diagram of the two rotating plates in the present invention in their original state;

[0034] Figure 9 It is a structural sectional view of the movable frame in the present invention.

[0035] In the figure: 1. base; 2. first neutralization barrel; 3. second neutralization barrel; 4. first motor; 5. third motor; 6. first water inlet; 7. steam outlet; 8. first outlet; 9. mounting plate; 10. first pipe; 11. second pipe; 12. second water inlet; 13. second outlet; 14. fixing plate; 15. sliding rod; 16. first rotating shaft; 17. first stirring blade; 18. third rotating shaft; 19. second stirring blade; 20. second motor; 21. sliding block; 22. movable frame; 23. cleaning brush; 24. second rotating shaft; 25. slide; 26. connecting end; 27. limiting groove; 28. circular groove; 29. ​​connecting rod; 30. limiting block; 31. fixing seat; 32. rotating plate; 33. drainage hole; 34. storage groove; 35. rectangular groove; 36. fourth motor; 37. winding wheel; 38. connecting rope DETAILED DESCRIPTION

[0036] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0037] Reference Figures 1-9 A multi-stage treatment method for manganese sulfate wastewater containing benzoquinone, the treatment method comprising the following steps:

[0038] Step 1: Leach out benzoquinone. First, measure the contents of manganese, sulfate, and ammonium sulfate in the manganese sulfate wastewater. Usually, the manganese sulfate content in the manganese sulfate wastewater is 45g / L, the ammonium salt is 35g / L, and the pH value is 1.5. Put the manganese sulfate wastewater and clean water in a ratio of 3:1 into the first neutralization barrel 2, and then heat and stir the mixed manganese sulfate wastewater. After the manganese sulfate wastewater is heated to 90°C, the benzoquinone in the manganese sulfate wastewater is evaporated with the steam. After the manganese sulfate wastewater is kept at 90°C and evaporated for 6 hours, the benzoquinone content is detected. After the benzoquinone content in the manganese sulfate wastewater is qualified, turn off the stirring and let it stand for 6 hours to allow the reacted manganese ore impurities in the wastewater to precipitate. The manganese sulfate wastewater above the precipitate in the first neutralization barrel 2 is pumped out by a water pump and discharged into the second neutralization barrel 3. The precipitate is then discharged into the filter press through the first discharge port 8, and is roughly pressed through the first filter press. The manganese sulfate wastewater after filtration enters the second neutralization barrel 3 through the second water inlet 12.

[0039] Step 2: Neutralize and remove iron and nickel. Open the Roots blower and the air duct valve of the second neutralization barrel 3 to aerate the manganese sulfate wastewater entering the second neutralization barrel 3. The aeration time is 60 minutes. At the same time, start adding ammonia water for neutralization. After adding ammonia water, when the pH value of the manganese sulfate wastewater reaches 5.9-6.0, turn off the ammonia water. After stirring for 30 minutes, qualitatively check whether the iron is qualified again. After the iron is qualified, ensure that the temperature of the manganese sulfate wastewater drops to between 35℃ and 38℃, and use precision test paper to detect when the pH value reaches 6.4-6.6. Confirm again that the temperature of the manganese sulfate wastewater in the second neutralization barrel 3 is between 35℃ and 38℃. After reaching the standard, sodium fumer is added in an amount of 0.17 kg per cubic meter. After the addition of sodium fumer, the manganese sulfate wastewater is stirred for 40 minutes, and then the nickel is qualitatively detected. The manganese sulfate wastewater is qualified if it contains no iron and no nickel, and samples are taken for quantitative testing. After the test is qualified, industrial activated carbon and polyacrylamide are added to the manganese sulfate wastewater, and the amount of industrial activated carbon added is 1 kg per cubic meter, and the amount of polyacrylamide added is 7 g per cubic meter. Then, the manganese sulfate wastewater is further stirred for 1 hour. After the adsorption of the industrial activated carbon and polyacrylamide in the manganese sulfate wastewater is completed, the stirring is turned off and the wastewater is allowed to stand for 5 hours for a second filter press.

[0040] Step 3: Sulfidation to remove zinc and organic matter. After the manganese sulfate wastewater is qualified, it is pressed into a sulfidation barrel. When the temperature of the manganese sulfate wastewater drops below 50°C, sulfuric acid or the anolyte after filter pressing or precipitation is added for secondary neutralization to reduce the pH value of the manganese sulfate wastewater to about 5.0. After the pH value is reduced, the manganese sulfate wastewater is stirred for 10 minutes and sampled to test the content of nickel, cobalt, zinc, and negative divalent sulfur. Then, 0.19 kg of sodium sulfide per cubic meter is added to remove zinc. If zinc sulfate rebound occurs, continue to add sodium sulfide for sulfidation treatment. After the various heavy metal indicators in the manganese sulfate wastewater are qualified, 14 g of polyacrylamide per cubic meter is added and stirred for 10 minutes. After the stirring is completed, it is precipitated for 5 hours. Finally, the manganese sulfate wastewater is subjected to a third filter press.

[0041] Step 4: Standing. After the third filter press, hydrogen peroxide is added at a rate of 0.07 kg per cubic meter to the manganese sulfate wastewater. After the addition of hydrogen peroxide, the manganese sulfate wastewater is allowed to stand for 24 hours. After the manganese sulfate wastewater has stood for the fourth fine filtration, the purification treatment of the manganese sulfate wastewater is completed.

[0042] As a technical optimization solution of the present invention, a multi-stage treatment device for manganese sulfate wastewater containing benzoquinone is provided, which is applied to the above-mentioned treatment method. The device includes a first neutralization barrel 2, a second neutralization barrel 3 and a base 1. The first neutralization barrel 2 and the second neutralization barrel 3 are both arranged on the top of the base 1. The top and bottom of the first neutralization barrel 2 are respectively provided with a first water inlet 6 and a first outlet 8. The top of the first neutralization barrel 2 is also provided with multiple steam outlets 7. The interior of the first neutralization barrel 2 is provided with a first stirring mechanism for stirring the manganese sulfate wastewater. The top and bottom of the second neutralization barrel 3 are respectively provided with a second water inlet 12 and a second outlet 13. The interior of the second neutralization barrel 3 is respectively provided with an auxiliary sampling mechanism and a second stirring mechanism for facilitating sampling of the manganese sulfate wastewater.

[0043] As a technical optimization solution of the present invention, a mounting plate 9 is installed between the first neutralization barrel 2 and the second neutralization barrel 3. A water pump is installed on top of the mounting plate 9. A first pipe 10 and a second pipe 11 are installed at the input and output ends of the water pump, respectively. The ends of the first pipe 10 and the second pipe 11 away from the water pump extend into the interiors of the first neutralization barrel 2 and the second neutralization barrel 3, respectively. The wastewater after sedimentation treatment in the first neutralization barrel 2 can be pumped out by the provided water pump and discharged through the second pipe 11 into the interior of the second neutralization barrel 3 for further treatment.

[0044] As a technical optimization solution of the present invention, the first stirring mechanism includes a first motor 4 mounted on the top of the first neutralization barrel 2. The output end of the first motor 4 passes through the first neutralization barrel 2 and is connected to a first rotating shaft 16. The outer wall of the first rotating shaft 16 is mounted with a plurality of first stirring blades 17. After starting, the first motor 4 can drive the first rotating shaft 16 and the plurality of first stirring blades 17 to rotate synchronously, stirring the wastewater inside the first neutralization barrel 2.

[0045] As a technical optimization solution of the present invention, the second stirring mechanism includes a second motor 20 mounted inside the base 1. The output end of the second motor 20 passes through the second neutralization barrel 3 and is connected to a second rotating shaft 24. The outer wall of the second rotating shaft 24 is mounted with a plurality of second stirring blades 19. After starting, the second motor 20 can drive the second rotating shaft 24 and the plurality of second stirring blades 19 to rotate synchronously, stirring the wastewater inside the second neutralization barrel 3.

[0046] As a technical optimization solution of the present invention, the auxiliary sampling mechanism includes a third motor 5 installed on the top of the second neutralization barrel 3. The output end of the third motor 5 passes through the second neutralization barrel 3 and is connected to the third rotating shaft 18. The outer wall of the third rotating shaft 18 is provided with a plurality of limiting grooves 27. A movable frame 22 is provided inside the second neutralization barrel 3. The movable frame 22 slides up and down inside the limiting grooves 27 through a plurality of limiting blocks 30 provided on the inner wall. After the third motor 5 is started, it can drive the third rotating shaft 18 to rotate inside the second neutralization barrel 3. Since the movable frame 22 is slidably connected to the limiting grooves 27 through the plurality of limiting blocks 30 provided inside, the third rotating shaft 18 can drive the movable frame 22 to rotate synchronously inside the second neutralization barrel 3 during the rotation process.

[0047] As a technical optimization solution of the present invention, two fixed plates 14 are installed on the top of the second neutralization barrel 3, and the outer walls of the two fixed plates 14 on the side close to each other are provided with sliding grooves 25, and sliders 21 are installed inside the two sliding grooves 25, and the bottom ends of the two sliders 21 are provided with sliding rods 15, and the bottom ends of the two sliding rods 15 are provided with connecting ends 26, and the top of the movable frame 22 is provided with a circular groove 28 that slides with the two connecting ends 26. Linear motors are preset inside the two slide grooves 25. The two linear motors can drive the two sliders 21 to move up and down inside the corresponding slide grooves 25, and drive the two slide bars 15 to slide up and down on the top of the second neutralizing barrel 3. Since the bottom ends of the two slide bars 15 are slidably connected to the circular grooves 28 on the top of the mobile frame 22, the two slide bars 15 can drive the mobile frame 22 to move up and down synchronously inside the second neutralizing barrel 3 during the up and down sliding process; since the two slide bars 15 are slidably connected to the mobile frame 22, when the third motor 5 drives the mobile frame 22 to rotate, the two slide bars 15 will not hinder the rotation of the mobile frame 22, ensuring that the rotation of the mobile frame 22 is not affected.

[0048] As a technical optimization solution of the present invention, two fixed seats 31 are installed at the bottom end of the mobile frame 22. Two rotating plates 32 are installed inside the two fixed seats 31 through a connecting shaft. The outer walls of both ends of the two connecting shafts are equipped with torsion springs. The interiors of the two rotating plates 32 are provided with a receiving groove 34. The bottom ends of the two rotating plates 32 are provided with a plurality of drainage holes 33 connected to the receiving groove 34. Figure 8 As shown, the two rotating plates 32 are originally in a vertical state inside the corresponding fixed seats 31. By pushing the bottom ends of the two rotating plates 32 upward, the deformation generated by the corresponding two torsion springs can be used to make the two rotating plates 32 rotate upward to a state parallel to the movable frame 22. After the restrictions on the two rotating plates 32 are released, the two rotating plates 32 are elastically restored with the help of the corresponding two torsion springs, so that the two rotating plates 32 can be rotated downward and restored to the original vertical state.

[0049] As a technical optimization solution of the present invention, a plurality of connecting rods 29 are mounted on the outer wall of the movable frame 22. A circular cleaning brush 23 is mounted on one end of the connecting rods 29 away from the movable frame 22. As the movable frame 22 moves up and down inside the second neutralization barrel 3, it drives the cleaning brush 23 to clean the inner wall of the second neutralization barrel 3.

[0050] As a technical optimization solution of the present invention, two rectangular slots 35 are defined within the interior of the mobile frame 22. A fourth motor 36 is mounted within each of the two rectangular slots 35. Winding wheels 37 are mounted at the output ends of the two fourth motors 36. Connecting ropes 38 are wound around the surfaces of the two winding wheels 37. The ends of the two connecting ropes 38, away from the winding wheels 37, are connected to the rotating plate 32 adjacent thereto. After activation, the two fourth motors 36 can drive the two winding wheels 37 to rotate, reeling in and unreeling the two connecting ropes 38. This allows the two connecting ropes 38 to pull and reset the two rotating plates 32, thereby automatically controlling the rotation and reset of the two rotating plates 32. The fourth motors 36 are waterproof motors, and a waterproof mechanism is provided within the rectangular slots 35 to prevent wastewater from entering the interior of the rectangular slots 35.

[0051] In this embodiment, valves are preset inside the first water inlet 6 , the second water inlet 12 , the first outlet 8 , the second outlet 13 , the first pipe 10 and the second pipe 11 .

[0052] In the present invention, when a user uses the device, wastewater and clean water are injected into the first neutralization barrel 2 through the first water inlet 6 in a ratio of 3:1, the heating mechanism inside the first neutralization barrel 2 is controlled to heat the wastewater, and the first stirring mechanism is controlled to stir the wastewater at the same time. Benzoquinone in the wastewater is discharged outward from multiple steam outlets 7 together with steam, until the benzoquinone content in the manganese sulfate wastewater is qualified, the first stirring mechanism is stopped, and the wastewater is allowed to stand for 6 hours to precipitate the reacted manganese ore impurities in the wastewater. The manganese sulfate wastewater above the precipitate in the first neutralization barrel 2 is pumped out by a water pump and discharged into the second neutralization barrel 3, and then the precipitate is discharged into the filter press through the first discharge port 8, and is roughly pressed through the first filter press. The manganese sulfate wastewater after filtration enters the second neutralization barrel 3 through the second water inlet 12.

[0053] The wastewater entering the second neutralization barrel 3 is aerated for 60 minutes, and then ammonia, sodium benzoate, industrial activated carbon and polyacrylamide are added. The second stirring mechanism is used to stir the wastewater, so that the industrial activated carbon and polyacrylamide adsorb the heavy metal substances in the wastewater. The second stirring mechanism is stopped, and the wastewater in the second neutralization barrel 3 is allowed to stand for 5 hours. It is then discharged through the second discharge port 13 into the filter press for the second filtration, thereby completing the first two steps of purification of the wastewater.

[0054] When the above-mentioned wastewater is in the second neutralization barrel 3 for relevant purification treatment, the staff needs to sample and test the wastewater on time to ensure that the relevant indicators in the wastewater are qualified. In order to facilitate the staff to quickly sample the wastewater, the two fourth motors 36 can be controlled to start together, drive the two winding wheels 37 to rotate, and reel in the two connecting ropes 38 together, pulling the two rotating plates 32 upward to a state parallel to the moving frame 22, and then controlling the two sliders 21 to slide downward together in the corresponding slide grooves 25, driving the two slide bars 15 to move downward together in the second neutralization barrel 3, pushing the moving frame 22 downward to the inside of the wastewater, and now the wastewater will enter the receiving grooves 34 inside the two rotating plates 32. After the wastewater enters the inside of the receiving groove 34, as The two sliders 21 move upward and reset inside the corresponding slide grooves 25, driving the movable frame 22 to move upward until it abuts against the top surface of the second neutralization barrel 3. At this time, one of the rotating plates 32 is located directly below the second water inlet 12. Since the multiple drainage holes 33 opened on the outer walls of the two rotating plates 32 are relatively small in diameter, the multiple drainage holes 33 at the bottom of the rotating plate 32 moved above the wastewater cannot quickly discharge the collected wastewater. The staff can insert the bottom end of the sampling test tube into one of the receiving grooves 34 through the second water inlet 12 to quickly sample the wastewater collected in the receiving groove 34, thereby avoiding the problem that the wastewater level inside the second neutralization barrel 3 is low and it is inconvenient to manually use a test tube for sampling, thereby improving the staff's sampling efficiency of wastewater and facilitating rapid testing of wastewater.

[0055] During the process of mixing and stirring the wastewater and other additives by the second stirring mechanism, a lot of foam will inevitably be generated on the water surface. In order to avoid the problem that the additives in the foam cannot be mixed in the wastewater, resulting in low reaction efficiency with the wastewater, the above steps can be repeated, so that the movable frame 22 is immersed in the wastewater again until the two receiving tanks 34 collect part of the wastewater, and then the movable frame 22 is controlled to move upward to above the wastewater. As the third motor 5 drives the movable frame 22 to rotate inside the second neutralization barrel 3, the multiple drainage holes 33 located at the bottom of the two rotating plates 32 can sprinkle the wastewater collected in the receiving tank 34 downward, defoam the foam on the wastewater surface, improve the efficiency of the mixing reaction between the additives and the wastewater, and facilitate the efficiency of purifying and removing harmful substances in the wastewater.

[0056] After the waste water in the second neutralization barrel 3 is discharged, in order to facilitate the subsequent use of the second neutralization barrel 3, the second neutralization barrel 3 needs to be cleaned to avoid the accumulation of some impurities in the second neutralization barrel 3. At this time, the two sliders 21 can be controlled to move up and down in the corresponding chute 25. With the help of the up and down movement of the two slide bars 15, the mobile frame 22 is driven to move up and down synchronously in the second neutralization barrel 3, so that the cleaning brush 23 provided on the outer wall of the mobile frame 22 can automatically clean the impurities attached to the inner wall of the second neutralization barrel 3 during the up and down movement.

[0057] The third motor 5 can also cooperate with the mobile frame 22 to rotate, so that the cleaning brush 23 can rotate and clean the inner wall of the second neutralization barrel 3, thereby improving the efficiency and quality of cleaning impurities on the inner wall of the second neutralization barrel 3;

[0058] When the cleaning brush 23 is used to clean the second neutralization barrel 3, the cleaning brush 23 is used to clean the second neutralization barrel 3. When the cleaning brush 23 is used to clean the second neutralization barrel 3, the cleaning brush 23 is used to clean the second neutralization barrel 3. When the cleaning brush 23 is used to clean the second neutralization barrel 3, the cleaning brush 23 is used to clean the second neutralization barrel 3. When the cleaning brush 23 is used to clean the second neutralization barrel 3, the cleaning brush 23 is used to clean the second neutralization barrel 3.

[0059] After the second neutralization barrel 3 has been used for a period of time, the two fourth motors 36 can be controlled to drive the two winding wheels 37 to rotate, driving the two connecting ropes 38 to reel in while pulling the two rotating plates 32 to rotate upward until they are parallel to the movable frame 22. At this time, the two fourth motors 36 are controlled to be de-energized, so that the two winding wheels 37 are no longer restricted, and the two rotating plates 32 are not limited by the pulling of the connecting ropes 38. With the help of the corresponding two torsion springs, the two rotating plates 32 are elastically reset, so that the two rotating plates 32 will rotate downward and reset at a faster speed. At this time, the two rotating plates 32 will knock on the inner wall of the second neutralization barrel 3 while rotating downward and resetting. The above operation is repeated many times, and the third motor 5 is controlled to drive the movable frame 22 and the two rotating plates 32 to adjust the position, so that the two rotating plates 32 can knock on different positions inside the second neutralization barrel 3 for detection. The staff can use relevant instruments or personal auditory experience to judge whether there is cracks or other damage inside the second neutralization barrel 3, so as to achieve the effect of automatic knocking detection of the second neutralization barrel 3, which is convenient for inspection and maintenance of the second neutralization barrel 3.

[0060] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to the specific embodiments described. Obviously, many modifications and variations are possible based on the content of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A multi-stage treatment method for manganese sulfate wastewater containing benzoquinone, characterized in that: The treatment method includes the following steps: Step 1: Leaching and removing benzoquinone, the wastewater and clean water are put into the first neutralization barrel (2) at a ratio of 3:1, and then the mixed manganese sulfate wastewater is heated and stirred. After the manganese sulfate wastewater is heated to 90°C, the benzoquinone in the manganese sulfate wastewater evaporates with the steam. Then the manganese sulfate wastewater is closed and stirred and allowed to stand for 6 hours, and the manganese sulfate wastewater is subjected to the first filter press; Step 2: Neutralization to remove iron and nickel. The manganese sulfate wastewater after the first filter press in step 1 is introduced into the second neutralization barrel (3) for aeration. Then, ammonia water, sodium benzoate, industrial activated carbon and polyacrylamide are added to the second neutralization barrel (3) in sequence. After mixing and stirring, the mixture is allowed to stand for 5 hours and then the second filter press is performed. Step 3: Sulfurization to remove zinc and organic matter. The manganese sulfate wastewater after the second filter press in step 2 is introduced into a sulfidation barrel. Sulfuric acid, sodium sulfide, and polyacrylamide are added to the sulfidation barrel in sequence. After mixing and stirring, the mixture is precipitated for 5 hours and then the third filter press is performed. Step 4: Standing, adding hydrogen peroxide to the manganese sulfate wastewater after the third filter press in step 3 and standing for 24 hours, and then performing the fourth fine filtration to complete the purification of the manganese sulfate wastewater; The method also adopts the following treatment device, comprising a first neutralization barrel (2), a second neutralization barrel (3) and a base (1), characterized in that the first neutralization barrel (2) and the second neutralization barrel (3) are both arranged on the top of the base (1), the top and bottom of the first neutralization barrel (2) are respectively provided with a first water inlet (6) and a first outlet (8), the top of the first neutralization barrel (2) is also provided with a plurality of steam outlets (7), the interior of the first neutralization barrel (2) is provided with a first stirring mechanism for stirring the manganese sulfate wastewater, the top and bottom of the second neutralization barrel (3) are respectively provided with a second water inlet (12) and a second outlet (13), and the interior of the second neutralization barrel (3) is respectively provided with an auxiliary sampling mechanism for facilitating sampling of the manganese sulfate wastewater and a second stirring mechanism; The auxiliary sampling mechanism comprises a third motor (5) mounted on the top of the second neutralization barrel (3); the output end of the third motor (5) passes through the second neutralization barrel (3) and is connected to a third rotating shaft (18); a plurality of limiting grooves (27) are provided on the outer wall of the third rotating shaft (18); a movable frame (22) is provided inside the second neutralization barrel (3); the movable frame (22) slides up and down inside the limiting grooves (27) via a plurality of limiting blocks (30) provided on the inner wall; Two fixed plates (14) are installed on the top of the second neutralization barrel (3), and a sliding groove (25) is provided on the outer wall of the two fixed plates (14) on the side close to each other. Slide blocks (21) are installed inside the two sliding grooves (25), and slide rods (15) are installed at the bottom ends of the two slide rods (21). Connecting ends (26) are installed at the bottom ends of the two slide rods (15), and a circular groove (28) is provided on the top of the movable frame (22) for sliding cooperation with the two connecting ends (26); Two fixed seats (31) are installed at the bottom end of the movable frame (22), and two rotating plates (32) are rotatably installed inside the two fixed seats (31) through connecting shafts. The outer walls of both ends of the two connecting shafts are both equipped with torsion springs. The insides of the two rotating plates (32) are each provided with a receiving groove (34), and the bottom ends of the two rotating plates (32) are each provided with a plurality of drainage holes (33) connected to the receiving grooves (34).

2. The multi-stage treatment method for manganese sulfate wastewater containing benzoquinone according to claim 1, characterized in that: A mounting plate (9) is installed between the first neutralization barrel (2) and the second neutralization barrel (3), a water pump is installed on the top of the mounting plate (9), a first pipe (10) and a second pipe (11) are installed at the input end and the output end of the water pump, respectively, and the ends of the first pipe (10) and the second pipe (11) away from the water pump extend into the interior of the first neutralization barrel (2) and the second neutralization barrel (3), respectively.

3. The multi-stage treatment method for manganese sulfate wastewater containing benzoquinone according to claim 2, characterized in that: The first stirring mechanism comprises a first motor (4) mounted on the top of the first neutralization barrel (2); an output end of the first motor (4) passes through the first neutralization barrel (2) and is connected to a first rotating shaft (16); and a plurality of first stirring blades (17) are mounted on the outer wall of the first rotating shaft (16).

4. The multi-stage treatment method for manganese sulfate wastewater containing benzoquinone according to claim 3, characterized in that: The second stirring mechanism comprises a second motor (20) installed inside the base (1); an output end of the second motor (20) passes through the second neutralization barrel (3) and is connected to a second rotating shaft (24); and a plurality of second stirring blades (19) are installed on the outer wall of the second rotating shaft (24).

5. The multi-stage treatment method for manganese sulfate wastewater containing benzoquinone according to claim 4, characterized in that: A plurality of connecting rods (29) are installed on the outer wall of the movable frame (22), and a circular cleaning brush (23) is commonly installed on one end of the plurality of connecting rods (29) away from the movable frame (22).

6. The multi-stage treatment method for manganese sulfate wastewater containing benzoquinone according to claim 5, characterized in that: Two rectangular slots (35) are provided inside the movable frame (22), and a fourth motor (36) is installed inside each of the two rectangular slots (35). A winding wheel (37) is installed at the output end of each of the two fourth motors (36). A connecting rope (38) is wound on the surface of each of the two winding wheels (37), and one end of each of the two connecting ropes (38) away from the winding wheel (37) is connected to a rotating plate (32) adjacent to the winding wheel (37).