3N electrolytic manganese metal additive adding system

Abstract

The utility model discloses an N electrolytic manganese metal additive adding system which comprises a control end and an electrolytic bath, the electrolytic bath is provided with a liquid inlet pipeline and a liquid outlet pipeline, the liquid inlet pipeline is communicated with the liquid outlet pipeline, a circulating pump is installed for liquid pumping circulation, the liquid inlet pipeline is communicated with a liquid distribution pipe arranged in the electrolytic bath through a water segregator, and the liquid distribution pipe is communicated with a liquid outlet pipeline. And the liquid outlet pipeline is communicated with a liquid return pipe arranged in the electrolytic bath through a water collector, and an additive adding system is arranged on the liquid outlet pipeline. According to the 3N electrolytic manganese metal additive adding method and the 3N electrolytic manganese metal additive adding system, the buffer tank is used as a transfer storage tank for urgently controlling the concentration of ammonium sulfite, and the purpose of stably controlling the addition of ammonium sulfite can be achieved by switching pipelines and enabling a bath solution to selectively enter the buffer tank for transfer.

Description

Technical Field

[0001] The utility model relates to a system for adding additives to 3N electrolytic metal manganese. Background Art

[0002] As downstream electrolytic manganese metal enterprises have higher and higher requirements for manganese purity, many enterprises have begun to study the production of high-purity manganese metal. At present, the preparation process of electrolytic refined high-purity manganese mainly adopts wet electrolysis. Manganese sulfate solution is obtained by acid leaching manganese ore. The solution enters the electrolytic cell for electrolysis after deep purification. During the electrolysis of manganese, additives need to be added to improve the current efficiency to obtain manganese plates with uniform particle size, flatness and brightness.

[0003] At present, there are many studies on electrolytic manganese additives, mainly involving two major categories: inorganic and organic, as well as some composite additives. Inorganic additives are mainly sulfur and sulfur compounds, and organic additives are mainly organic composite additives containing unsaturated bonds such as C=C, C=0, C=S, N=N, such as polyacrylamide, polyethylenediamine, citric acid, thiourea, etc. There are many relevant literature reports on this type of additives, but there is no additive that can completely replace selenium dioxide, and many of them are only in the laboratory research stage and cannot be used in industrial production.

[0004] According to research, ammonium sulfite is added in the production of electrolytic manganese metal to completely replace selenium dioxide for use in the electrolytic system. There are two main problems in the preparation of 3N electrolytic manganese metal: (1) The impurity content of industrial-grade sulfurous acid is relatively high. If too much is added, the Fe content and C content of the electrolytic manganese metal will increase, affecting the purity of the manganese metal; (2) The stability of ammonium sulfite is poor. When added to the neutral manganese sulfate liquid tank, the residence time is too long and it is very easy to react with the oxidizing substances in the neutral manganese sulfate solution, resulting in a large deviation between the theoretical value and the actual measured value of ammonium sulfite in the neutral manganese sulfate solution. It is necessary to add more ammonium sulfite additives to prepare 3N electrolytic manganese metal with industrial ammonium sulfite in a more efficient, high-quality and stable manner. Therefore, this application is proposed. Utility Model Content

[0005] The purpose of the utility model is to provide a 3N electrolytic manganese metal additive adding system to solve the problems raised in the above background technology.

[0006] In order to achieve the above purpose, the utility model provides the following technical solutions:

[0007] A N electrolytic manganese metal additive adding system comprises a control end and an electrolytic cell, wherein the electrolytic cell is provided with a liquid inlet pipeline and a liquid outlet pipeline, the liquid inlet pipeline and the liquid outlet pipeline are connected, and a circulating pump is installed to circulate the liquid, the liquid inlet pipeline is connected with a liquid distribution pipe arranged in the electrolytic cell through a water distributor, the liquid outlet pipeline is connected with a liquid return pipe arranged in the electrolytic cell through a water collector, and an additive adding system is arranged on the liquid outlet pipeline.

[0008] As a further solution of the utility model: the additive adding system mainly consists of a liquid outlet pipeline and an additive tank, the liquid outlet pipeline is installed with the additive tank through a liquid adding pipeline, and a peristaltic pump is installed on the liquid adding pipeline.

[0009] As a further solution of the utility model: the liquid adding pipeline is provided with a one-way valve to prevent the fluid in the liquid outlet pipeline from flowing into the liquid adding pipeline, and the additive tank is equipped with a liquid level meter.

[0010] As a further solution of the utility model: the output end of the liquid outlet pipeline is connected to the circulation pipeline and the buffer tank respectively through a three-way valve, the circulation pipeline is connected to the liquid inlet pipeline, the liquid outlet end of the buffer tank is connected to the liquid inlet pipeline through a variable frequency liquid pump and a return liquid pipeline, and both the return liquid pipeline and the circulation pipeline are provided with a one-way valve.

[0011] As a further solution of the utility model: a partition is provided inside the buffer tank, which separates the buffer tank into two upper and lower chambers, the top chamber is a fusion chamber, and the bottom chamber is a liquid discharge chamber, and a neck tube is provided at the bottom of the partition.

[0012] As a further solution of the utility model: a constant pressure pipeline is arranged on the top of the buffer tank.

[0013] As a further solution of the utility model: an ammonium sulfate concentration online detector is installed on the liquid outlet pipeline, and the ammonium sulfate concentration online detector is electrically connected to the control end. The control end controls the circulation pump, peristaltic pump, variable frequency liquid pump and three-way valve through the detection value of the ammonium sulfate concentration online detector.

[0014] Compared with the prior art, the beneficial effects of the utility model are:

[0015] The 3N electrolytic manganese metal additive adding method and the adding system thereof use the 3N electrolytic manganese metal additive adding system and a buffer tank as a transfer storage tank to urgently control the concentration of ammonium sulfite. The tank liquid can selectively enter the buffer tank for transfer by switching the pipeline, thereby achieving the purpose of stably controlling the addition of ammonium sulfite. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 A schematic diagram of a 3N electrolytic manganese metal additive adding system;

[0017] Figure 2 This is a logical relationship diagram of the control end in a 3N electrolytic manganese metal additive system.

[0018] In the figure: 1. electrolytic cell; 2. liquid distribution pipe; 3. water distributor; 4. liquid inlet valve; 5. liquid inlet pipeline; 6. circulation pipeline; 7. variable frequency liquid pump; 8. buffer tank; 9. three-way valve; 10. constant pressure pipeline; 11. liquid return pipe; 12. water collector; 13. ammonium sulfate concentration online detector; 14. liquid outlet pipeline; 15. circulation pump; 16. additive tank; 17. peristaltic pump; 18. liquid adding pipeline; 19. partition; 20. liquid return pipeline. DETAILED DESCRIPTION

[0019] See also Figure 1 and 2In the embodiment of the utility model, a 3N electrolytic manganese metal additive adding system includes a 3N electrolytic manganese metal additive adding system that controls the addition of ammonium sulfite solution in a 3N electrolytic manganese metal additive adding method. The 3N electrolytic manganese metal additive adding system includes a control end and an electrolytic cell 1. The electrolytic cell 1 is provided with a liquid inlet pipeline 5 and a liquid outlet pipeline 14. The liquid inlet pipeline 5 and the liquid outlet pipeline 14 are connected, and a circulating pump 15 is installed to perform liquid circulation. The liquid inlet pipeline 5 is connected to a liquid distribution pipe 2 provided in the electrolytic cell 1 through a water distributor 3, and the liquid outlet pipeline 14 is connected to the electrolytic cell 1 through a water collector 12. The return pipe 11 arranged inside is connected, the liquid outlet pipeline 14 is provided with an additive adding system, and a liquid inlet valve 4 is also installed between the liquid inlet pipeline 5 and the water divider 3 to control the flow rate. The method for adding ammonium sulfite to completely replace selenium dioxide for electrolysis in the production of electrolytic manganese metal is as follows; the first step is to prepare a neutral manganese sulfate solution, after the manganese carbonate ore powder is acid-dissolved, sodium fumei, barium sulfide and other purifiers are added to remove impurities and purify the manganese sulfate solution to collect acid, and the pH is controlled at 6.0-6.5, and then air is passed to remove iron, and the manganese sulfate solution after filter pressing is neutralized with ammonia water, and the pH value of the solution is adjusted to prepare a qualified manganese sulfate electrolyte. The pH value control range of the electrolytic solution is: 6.7~7.5; the Mn2+ concentration requirement in the solution is: 25.00~40.00g / L; the ammonium sulfate concentration is: 80.00g / L~110.00g / L; the impurity content requirements: the content of zinc, cobalt, nickel, iron, copper, chromium, chromium, lead, selenium, and silicon are all less than 1mg / L, the potassium content is less than 15mg / L, the sodium content is less than 4g / L, the calcium content is less than 1g / L, and the magnesium content is less than 25g / L. The second step is the preparation of ammonium sulfite additives, using industrial grade ammonium sulfite with a sulfurous acid content of 85%.The preparation requirements of the ammonium sulfite aqueous solution are that the mass ratio of ammonium sulfite to pure water is: 2:25~50; the prepared ammonium sulfite solution is adjusted to pH 7.5~8.0 with ammonia water at room temperature to precipitate iron impurities in the solution, and then filtered. The filtered ammonium sulfite aqueous solution is used as an electrolytic additive. The third step is manganese electrolysis. 3N electrolysis of manganese metal adopts diaphragm bag electrolysis; electrolytic cell bath pH: 7.0~8.0; current density: 250~350A / m2; electrolytic cell bath temperature: 30.0℃~40.0℃; electrolytic cell manganese: 10.0g / L~15.0g / L; ammonium sulfite concentration requirement in the electrolytic cell bath: 0.1~0.2g / L; ammonium sulfite solution addition method: a small peristaltic pump is used to drop the ammonium sulfite solution at the inlet of the manganese sulfate electrolyte in the electrolytic cell, and the ammonium sulfite inlet speed is 0.5~2 L / h, ensuring that the concentration of ammonium sulfite in the bath is 0.1-0.2g / L, the purity of the prepared high-purity manganese is ≥99.97%, the surface of the high-purity manganese is flat and burr-free, this patent mainly uses sulfur-containing inorganic additive ammonium sulfite to completely replace selenium dioxide for the electrolysis system, prepares 3N electrolytic manganese metal, and improves the purity of electrolytic manganese metal. The neutral liquid after acid dissolution, impurity removal and filtration of Ghanaian manganese carbonate ore powder is used, and an appropriate amount of ammonium sulfite is added to the neutral liquid and then directly enters the electrolysis system for electrolysis. Due to the instability of ammonium sulfite, part of the ammonium sulfite reacts in the neutral liquid, resulting in a large deviation between the ammonium sulfite content and the theoretical value, the unstable electrolytic cell condition, and the low purity of the manganese flakes. The problem arises, and the method of adding ammonium sulfite is improved. The method of adding ammonium sulfite is changed to uniformly distribute it at the liquid inlet port of the electrolytic cell and then add the ammonium sulfite aqueous solution dropwise, and the liquid is evenly delivered in the form of a liquid distribution pipe 2. The electrolytic cell liquid is circulated to accelerate mixing, and the electrolytic cell liquid is kept uniform. The water collector 12 keeps the liquid inlet of the return pipe 11 uniform, and the concentration and liquid inlet speed of the ammonium sulfite aqueous solution are controlled to achieve a stable ammonium sulfite content in the electrolytic cell and a stable electrolytic cell condition. The amount of additives added is reduced to avoid the introduction of impurities, and at the same time, the residence time of ammonium sulfite in the liquid is reduced to reduce the oxidation-reduction reaction. Finally, the purity of 3N electrolytic manganese metal is improved, and the manganese metal content reaches 99.97%.

[0020] In a preferred embodiment, the additive adding system mainly consists of a liquid outlet pipeline 14 and an additive tank 16. The liquid outlet pipeline 14 is installed with the additive tank 16 through a liquid adding pipeline 18. A peristaltic pump 17 is installed on the liquid adding pipeline 18. The peristaltic pump 17 adds additives to the liquid outlet pipeline 14 through the liquid adding pipeline 18 at a uniform speed. The peristaltic pump 17 drips the ammonium sulfite solution. The ammonium sulfite inlet speed is 0.5~2 L / h to ensure that the ammonium sulfite concentration in the tank liquid is 0.1~0.2g / L. The liquid adding pipeline 18 is provided with a one-way valve to prevent the fluid in the liquid outlet pipeline 14 from flowing into the liquid adding pipeline 18, and the additive tank 16 is equipped with a liquid level meter.

[0021] In a preferred embodiment, the output end of the liquid outlet pipeline 14 is connected to the circulation pipeline 6 and the buffer tank 8 respectively through the three-way valve 9, a constant pressure pipeline 10 is arranged on the top of the buffer tank 8, the airflow can freely enter and exit through the constant pressure pipeline 10, the circulation pipeline 6 is connected with the liquid inlet pipeline 5, the liquid outlet end of the buffer tank 8 is connected with the liquid inlet pipeline 5 through the variable frequency liquid pump 7 and the liquid return pipeline 20, the liquid return pipeline 20 and the circulation pipeline 6 are both provided with a one-way valve, and a partition 19 is arranged inside the buffer tank 8, the partition 19 separates the buffer tank 8 into two upper and lower chambers, the top chamber is a fusion chamber, and the bottom chamber is a liquid discharge chamber. A neck tube is provided at the bottom of the partition 19. The three-way valve 9 can be switched to allow the circulating electrolytic cell liquid to selectively enter the circulation pipeline 6 or the buffer tank 8. When the additive adding system is not in operation or the concentration of ammonium sulfite in the cell liquid is within a controllable range, the circulating electrolytic cell liquid can selectively enter the circulation pipeline 6. When the concentration of ammonium sulfite in the cell liquid is close to the peak value or the valley value of the range, the circulating electrolytic cell liquid can selectively enter the buffer tank 8 to prevent the concentration of ammonium sulfite in the cell liquid from exceeding the critical value. By changing the operating efficiency of the circulation pump 15 and the peristaltic pump 17, the ammonium sulfite inlet speed is adjusted to 0.5-2 L / h so that its concentration reaches the range value, and then it is sent back to the electrolytic cell 1 through the return liquid pipeline 20. While achieving buffering, the controllability of the ammonium sulfite concentration is improved. The partition 19 divides the buffer tank 8 into two upper and lower chambers, and the fusion chamber is mixed. After the discharge chamber discharges the liquid, the cell liquid in the fusion chamber automatically enters the discharge chamber.

[0022] In a preferred embodiment, an ammonium sulfate concentration online detector 13 is installed on the liquid outlet pipeline 14, and the ammonium sulfate concentration online detector 13 is connected to the control end by electrical signals. The control end controls the circulating pump 15, the peristaltic pump 17, the variable frequency liquid pump 7 and the three-way valve 9 through the detection value of the ammonium sulfate concentration online detector 13, so as to realize an automated control scheme and meet the needs of modern intelligent production. In this application, the method of adding ammonium sulfite is changed from adding it into the neutral manganese sulfate liquid tank to dripping an ammonium sulfite aqueous solution at the liquid inlet port of the electrolytic cell, and the concentration and liquid inlet speed of the ammonium sulfite aqueous solution are controlled to achieve a stable ammonium sulfite content in the electrolytic cell and a stable electrolytic cell condition, reduce the amount of additives added to avoid the introduction of impurities, and reduce the ammonium sulfite residence time in the liquid for too long to cause redox reaction. By changing the addition method, a small amount of ammonium sulfite can be added to achieve the purpose of stabilizing the ammonium sulfite content in the tank liquid, thereby reducing the amount of additives used, improving the purity of 3N electrolytic manganese metal, and realizing that ammonium sulfite completely replaces selenium dioxide for the electrolytic system to produce 3N manganese metal.

[0023] It should be noted that the above embodiments all belong to the same utility model concept, and the description of each embodiment has its own focus. For matters that are not described in detail in some embodiments, reference can be made to the description in other embodiments.

[0024] The above-mentioned embodiments only express the implementation methods of the utility model, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the utility model patent. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the utility model, and these all belong to the protection scope of the utility model. Therefore, the protection scope of the utility model patent shall be based on the attached claims.

Claims

1. A 3N electrolytic manganese metal additive addition system, comprising a control end and an electrolytic cell (1), wherein the electrolytic cell (1) is provided with a liquid inlet pipeline (5) and a liquid outlet pipeline (14), wherein the liquid inlet pipeline (5) and the liquid outlet pipeline (14) are connected, and a circulation pump (15) is installed for liquid circulation, characterized in that: The liquid inlet pipeline (5) is connected to a liquid distribution pipe (2) provided in the electrolytic cell (1) through a water distributor (3), and the liquid outlet pipeline (14) is connected to a liquid return pipe (11) provided in the electrolytic cell (1) through a water collector (12). An additive adding system is provided on the liquid outlet pipeline (14).

2. A 3N electrolytic manganese metal additive adding system according to claim 1, characterized in that: The additive adding system mainly comprises a liquid outlet pipeline (14) and an additive tank (16); the liquid outlet pipeline (14) is connected to the additive tank (16) via a liquid adding pipeline (18); and a peristaltic pump (17) is installed on the liquid adding pipeline (18).

3. A 3N electrolytic manganese metal additive adding system according to claim 2, characterized in that: The liquid adding pipeline (18) is provided with a one-way valve for preventing the fluid in the liquid outlet pipeline (14) from flowing into the liquid adding pipeline (18), and the additive tank (16) is provided with a liquid level meter.

4. A 3N electrolytic manganese metal additive adding system according to claim 2 or 3, characterized in that: The output end of the liquid outlet pipeline (14) is respectively connected to the circulation pipeline (6) and the buffer tank (8) via a three-way valve (9); the circulation pipeline (6) is connected to the liquid inlet pipeline (5); the liquid outlet end of the buffer tank (8) is connected to the liquid inlet pipeline (5) via a variable frequency liquid pump (7) and a liquid return pipeline (20); and both the liquid return pipeline (20) and the circulation pipeline (6) are provided with a one-way valve.

5. A 3N electrolytic manganese metal additive adding system according to claim 4, characterized in that: The buffer tank (8) is provided with a partition (19) inside, the partition (19) divides the buffer tank (8) into two upper and lower chambers, the top chamber being a fusion chamber, and the bottom chamber being a liquid discharge chamber, and a neck tube is provided at the bottom of the partition (19).

6. A 3N electrolytic manganese metal additive adding system according to claim 5, characterized in that: A constant pressure pipeline (10) is provided on the top of the buffer tank (8).

7. A 3N electrolytic manganese metal additive adding system according to claim 4, characterized in that: An ammonium sulfate concentration online detector (13) is installed on the liquid outlet pipeline (14). The ammonium sulfate concentration online detector (13) is electrically connected to the control end. The control end controls the circulation pump (15), the peristaltic pump (17), the variable frequency liquid pump (7) and the three-way valve (9) according to the detection value of the ammonium sulfate concentration online detector (13).

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