Method and system for adding 3N electrolytic manganese metal additive

Abstract

The invention discloses a method and a system for adding a 3N electrolytic manganese metal additive. The method comprises the steps that S1, a manganese sulfate neutral solution is prepared, after manganese carbonate ore powder is subjected to acid dissolution, sodium dimethyl dithiocarbamate and a barium sulfide purifying agent are added to conduct impurity removal, purification and acid collection on the manganese sulfate solution, then air is introduced to remove iron, the manganese sulfate solution obtained after filter pressing is neutralized with ammonia water, the pH value of the solution is adjusted, and the qualified manganese sulfate electrolyte is prepared. According to the 3N electrolytic manganese metal additive adding method and system, an ammonium sulfite adding method is changed from adding in a manganese sulfate neutral liquid tank to dropwise adding an ammonium sulfite aqueous solution at a liquid inlet port of an electrolytic bath, and the concentration and the liquid inlet speed of the ammonium sulfite aqueous solution are controlled, so that the content of ammonium sulfite in the electrolytic bath is stable, and the condition of the electrolytic bath is stable; the addition amount of the additive is reduced, introduction of impurities is avoided, and meanwhile, oxidation-reduction reaction caused by too long retention time of ammonium sulfite in the liquid is reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of 3N electrolytic manganese metal additive adding method and its adding system. BACKGROUND

[0002] With the downstream enterprise of electrolytic manganese metal to the manganese purity requirement more and more high, many enterprises begin to study production high purity metal manganese, the preparation process of electrolytic refining high purity manganese at present mainly still adopts wet electrolysis, with manganese ore is obtained after acid leaching manganese sulfate solution, solution is entered into electrolytic cell electrolysis after depth purification, manganese needs to be added in the process of electrolysis Additive improves current efficiency, obtains the manganese plate of uniform particle size, flat and bright.

[0003] At present, the research of electrolytic manganese additive is much, mainly involves two major categories of inorganic and organic, and some composite additives, inorganic additive is mainly sulfur and sulfur compound, organic additive is mainly organic composite additive containing C=C, C=0, C=S, N=N etc. Unsaturated bond is main body, such as polyacrylamide, polyethylene diamine, citric acid, thiourea etc., there are many related literature reports about this kind of additive, but there is no one kind of additive can completely replace selenium dioxide, many are only in laboratory research stage, can not be applied to industrial production, therefore, the above problems need to be solved urgently. SUMMARY

[0004] The purpose of the present application is to provide a kind of 3N electrolytic manganese metal additive adding method and its adding system, to solve the problems raised in the above background.

[0005] To achieve the above object, the present application provides the following technical scheme: A kind of 3N electrolytic manganese metal additive adding method, comprising the following steps: S1: manganese sulfate neutral solution preparation, after acid solution of manganese carbonate ore powder, adding naftal sodium, barium sulfide purifying agent to the impurity removal and purification of manganese sulfate solution, then air is excluded iron, the neutralization of the manganese sulfate solution after pressure filtration is carried out with ammonia water, adjust the pH value of solution, prepare qualified manganese sulfate electrolyte; S2: ammonium sulfite additive preparation, using industrial grade ammonium sulfite, the content of sulfurous acid is 85%, ammonium sulfite is mixed with pure water to prepare ammonium sulfite aqueous solution;The prepared ammonium sulfite solution is adjusted to pH at room temperature with ammonia water, then the iron impurities in the solution are precipitated, and then filtered, and the filtered ammonium sulfite aqueous solution is used as electrolytic additive; S3: metal manganese electrolysis, 3N electrolytic manganese metal adopts diaphragm bag electrolysis, ammonium sulfite solution is added, ammonium sulfite solution is added by small peristaltic pump at the inlet of electrolytic cell manganese sulfate electrolyte, the concentration of ammonium sulfite in the tank solution is controlled, high purity manganese is prepared, and the surface of high purity manganese is flat without burr.

[0006] As a further scheme of the present application: the purifying agent in S1 removes impurities and purifies the manganese sulfate solution to collect acid, the pH is controlled at 6.0-6.5, the pH value of the electrolysis solution is controlled in the range of 6.7-7.5; the concentration of Mn 2+ in the solution is required to be 25.00-40.00 g / L; the concentration of ammonium sulfate is 80.00 g / L-110.00 g / L; the impurity content is required to be less than 1 mg / L for zinc, cobalt, nickel, iron, copper, chromium, chromium, lead, selenium and silicon, less than 15 mg / L for potassium, less than 4 g / L for sodium, less than 1 g / L for calcium and less than 25 g / L for magnesium.

[0007] As a further scheme of the present application: the mass ratio of ammonium sulfite to pure water in S2 is 2:25-50; the prepared ammonium sulfite solution is adjusted to pH 7.5-8.0 at room temperature with ammonia water, the iron impurities in the solution are precipitated, and then filtered, and the filtered ammonium sulfite aqueous solution is used as an electrolysis additive.

[0008] As a further scheme of the present application: the pH of the electrolytic tank solution in S3 is 7.0-8.0; the current density is 250-350 A / m 2 ; the electrolytic tank temperature is 30.0-40.0℃; the electrolytic tank manganese is 10.0-15.0 g / L; the concentration of ammonium sulfite in the electrolytic tank solution is required to be 0.1-0.2 g / L; the ammonium sulfite liquid speed is 0.5-2 L / h, which ensures that the concentration of ammonium sulfite in the solution is 0.1-0.2 g / L, and the prepared high-purity manganese purity is ≥99.97%.

[0009] A 3N electrolytic manganese metal additive adding system includes a N electrolytic manganese metal additive adding method for controlling the addition of ammonium sulfite solution, the N electrolytic manganese metal additive adding system includes a control end and an electrolytic tank, the electrolytic tank is provided with an inlet pipeline and an outlet pipeline, the inlet pipeline and the outlet pipeline are communicated, and a circulating pump is installed to circulate the liquid, the inlet pipeline is communicated with a liquid distribution pipe arranged in the electrolytic tank through a water distributor, the outlet pipeline is communicated with a liquid return pipe arranged in the electrolytic tank through a water collector, and an additive adding system is arranged on the outlet pipeline.

[0010] As a further scheme of the present application: the additive adding system mainly includes an outlet pipeline and an additive tank, the outlet pipeline is installed with the additive tank through a liquid adding pipeline, and a peristaltic pump is installed on the liquid adding pipeline.

[0011] As a further scheme of the present application: a one-way valve is arranged on the liquid adding pipeline to prevent the fluid in the outlet pipeline from flowing to the liquid adding pipeline, and a liquid level meter is arranged on the additive tank.

[0012] As a further scheme of the present application: the output end of the liquid outlet pipeline is communicated with the circulating pipeline and the buffer tank through a three-way valve, the circulating pipeline is communicated with the liquid inlet pipeline, the liquid outlet end of the buffer tank is communicated with the liquid inlet pipeline through a variable frequency liquid pump and a liquid return pipeline, and the liquid return pipeline is provided with a one-way valve.

[0013] As a further scheme of the present application: the inside of the buffer tank is provided with a partition layer, the partition layer divides the buffer tank into two chambers, the top chamber is a fusion chamber, and the bottom chamber is a liquid discharge chamber, and the bottom of the partition layer is provided with a neck pipe.

[0014] As a further scheme of the present application: an ammonium sulfate concentration on-line detector is installed on the liquid outlet pipeline, the ammonium sulfate concentration on-line detector is electrically connected with a control end, and the control end controls the circulating pump, the peristaltic pump, the variable frequency liquid pump and the three-way valve through the detection value of the ammonium sulfate concentration on-line detector.

[0015] Compared with the prior art, the present application has the following beneficial effects: 1. The 3N electrolytic manganese metal additive adding method and adding system, the adding method of ammonium sulfite is changed from adding in the manganese sulfate neutral liquid tank to dropping ammonium sulfite aqueous solution at the liquid inlet port of the electrolytic cell, the concentration and liquid inlet speed of the ammonium sulfite aqueous solution are controlled, the content of ammonium sulfite in the electrolytic cell is stabilized, the electrolytic cell is stable, the amount of additive is reduced to avoid the introduction of impurities, and the residence time of ammonium sulfite in the liquid is reduced to avoid redox reaction.

[0016] 2. The 3N electrolytic manganese metal additive adding method and adding system, through the change of the adding method, a small amount of ammonium sulfite can achieve the purpose of stabilizing the content of ammonium sulfite in the electrolyte, thereby reducing the amount of additive, improving the purity of 3N electrolytic manganese metal, and realizing that ammonium sulfite completely replaces selenium dioxide for producing 3N manganese metal in the electrolytic system.

[0017] 3. The 3N electrolytic manganese metal additive adding method and adding system, through the 3N electrolytic manganese metal additive adding system, the buffer tank is used as a transfer storage tank for emergency control of the concentration of ammonium sulfite, and the electrolyte can be selectively transferred into the buffer tank through a switching pipeline, so as to achieve the purpose of stabilizing the addition of ammonium sulfite. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 It is a flowchart of a 3N electrolytic manganese metal additive adding method and adding system; Figure 2 It is a schematic diagram of a 3N electrolytic manganese metal additive adding system in a 3N electrolytic manganese metal additive adding method and adding system; Figure 3The application relates to a 3N electrolytic manganese metal additive adding method and a logic relation diagram of a control end in an adding system thereof.

[0019] In the figure: 1, an electrolytic cell; 2, a liquid distribution pipe; 3, a water distributor; 4, a liquid inlet valve; 5, a liquid inlet pipeline; 6, a circulating pipeline; 7, a variable frequency liquid pump; 8, a buffer tank; 9, a three-way valve; 10, a constant pressure pipeline; 11, a liquid return pipe; 12, a water collector; 13, an ammonium sulfate concentration on-line detector; 14, a liquid outlet pipeline; 15, a circulating pump; 16, an additive tank; 17, a peristaltic pump; 18, a liquid adding pipeline; 19, a partition layer; and 20, a liquid return pipeline. DETAILED DESCRIPTION

[0020] Example I The application relates to a 3N electrolytic manganese metal additive adding method and a logic relation diagram of a control end in an adding system thereof. S1: Neutral manganese sulfate solution preparation, after the manganese carbonate ore powder is dissolved by acid, 0.30g / L of thiram and 0.10g / L of barium sulfide are added to the manganese sulfate solution to remove impurities, the acid is collected by roasting powder and double-flying powder, the pH value is controlled to be 6.0-6.5, then air is introduced to remove iron, the manganese sulfate solution after pressure filtration is neutralized by ammonia water, the solution pH value is adjusted, qualified manganese sulfate electrolyte is prepared, the pH value of the manganese sulfate electrolyte is 6.7, the Mn 2+ concentration is 36.2g / L, and the ammonium sulfate concentration is 85g / L. The impurity detection results of the manganese sulfate electrolyte are as follows: S2: Ammonium sulfite aqueous solution preparation: the mass ratio of ammonium sulfite to pure water is 2:50, 2kg of 85% industrial grade ammonium sulfite is dissolved in 50L of pure water, the solution is uniformly stirred, the pH value is adjusted to 7.5 at room temperature by using ammonia water, iron impurities in the solution are precipitated, then the solution is filtered, and the filtered ammonium sulfite aqueous solution is used as an additive in the electrolysis process, the ammonium sulfite concentration is 34g / L. S3: 3N metal manganese is prepared by using a diaphragm bag electrolysis method, the electrolytic cell solution pH value is controlled to be 7.0-7.5, the current density is 300A / m2, the electrolytic cell solution temperature is controlled to be 36-37 DEG C, the electrolytic cell manganese concentration is controlled to be 10.0g / L-11.0g / L, the electrolysis period is 24h, and the ammonium sulfite concentration in the electrolytic cell solution is required to be 0.1g / L. The ammonium sulfite solution adding method in the electrolysis process is that a small peristaltic pump is used to drop the ammonium sulfite solution at the manganese sulfate electrolyte inlet of the electrolytic cell, the ammonium sulfite liquid inlet speed is 0.685L / h, the ammonium sulfite concentration in the solution is ensured to be 0.1+ / -0.01g / L, the prepared high-purity manganese purity is greater than or equal to 99.97%, the high-purity manganese surface is smooth without burrs, and the high-purity manganese meets the requirements of the DJMnA brand 3N metal manganese in the YB / T051-2023 industry standard.

[0021] 3N electrolytic manganese metal detection results as follows: Example two A 3N electrolytic manganese metal additive adding method, characterized in that, comprising the following steps: S1: Manganese sulfate neutral solution preparation, after manganese carbonate ore powder is dissolved with acid, sodium formaldehyde sulfoxylate 0.30g / L, barium sulfide 0.10g / L, polymeric ferric sulfate 0.6g / L are added to the manganese sulfate solution to remove impurities, and the pH is controlled at 6.0-6.5, then air is passed to remove iron, and the filtered manganese sulfate solution is neutralized with ammonia water to adjust the pH of the solution. The pH of the manganese sulfate electrolyte is 6.7; the concentration of Mn 2+ is 38g / L; the concentration of ammonium sulfate is 82.5g / L; The impurity detection results of the manganese sulfate electrolyte are as follows: S2: Ammonium sulfite aqueous solution preparation: ammonium sulfite aqueous solution preparation: ammonium sulfite and pure water mass ratio 2:40, 2kg of 85% industrial grade ammonium sulfite is dissolved in 40L of pure water, stirred uniformly, then adjusted to pH 7.6 with ammonia water at room temperature, precipitated the iron impurities in the solution, then filtered, and the filtered ammonium sulfite aqueous solution is used as an additive in the electrolysis process, the concentration of ammonium sulfite is 42.5g / L.

[0022] S3: Diaphragm bag electrolysis is used to prepare 3N metal manganese, the electrolyte pH of the electrolytic cell is controlled at 7.0-7.8; the current density is 280A / m2; the electrolytic cell temperature is controlled at 37-38℃; the electrolytic cell manganese is controlled at 11.0g / L-12.0g / L; the electrolysis cycle is 24h; the ammonium sulfite concentration in the electrolyte of the electrolytic cell is required to be 0.1g / L; The ammonium sulfite solution adding method in the electrolysis process: a small peristaltic pump is used to add ammonium sulfite solution at the inlet of the manganese sulfate electrolyte of the electrolytic cell, the ammonium sulfite solution adding speed is 0.548L / h, the ammonium sulfite concentration in the electrolyte is ensured to be 0.1±0.01g / L, the prepared high-purity manganese purity is ≥99.97%, the high-purity manganese surface is smooth without burrs, which meets the requirements of DJMnA brand 3N metal manganese in YB / T051-2023 industry standard.

[0023] 3N electrolytic manganese metal detection results as follows: Example three A 3N electrolytic manganese metal additive adding method, characterized in that, comprising the following steps: S1: Manganese sulfate neutral solution preparation, after the manganese carbonate ore powder is dissolved with acid, 0.30 g / L of thiram, 0.10 g / L of barium sulfide, 0.6 g / L of polymeric ferric sulfate, 0.4 g / L of manganese dioxide are added to the manganese sulfate solution to remove impurities, the acid is collected by roasting powder and double fly powder, the pH is controlled at 6.0-6.5, then air is passed to remove iron, the manganese sulfate solution after pressure filtration is neutralized with ammonia water, and the pH of the solution is adjusted. The pH of the manganese sulfate electrolyte is 6.7; the concentration of Mn 2+ is 37.2 g / L; the concentration of ammonium sulfate is 80 g / L; The impurity detection results of the manganese sulfate electrolyte are as follows: S2: Ammonium sulfite aqueous solution preparation: ammonium sulfite aqueous solution preparation: ammonium sulfite and pure water mass ratio 2:40, 2 kg of 85% industrial grade ammonium sulfite is dissolved in 40 L of pure water, stirred uniformly, then adjusted to pH 8.0 with ammonia water at room temperature, precipitated the iron impurities in the solution, then filtered, the filtered ammonium sulfite aqueous solution is used as an additive in the electrolysis process, and the concentration of ammonium sulfite is 68 g / L.

[0024] S3: 3N manganese metal is prepared by diaphragm bag electrolysis, the electrolyte pH of the electrolytic cell is controlled at 7.5-8.0; the current density is 320 A / m2; the electrolytic cell temperature is controlled at 35-36℃; the electrolytic cell manganese is controlled at 10.5 g / L-11.5 g / L; the electrolysis period is 24 h; the ammonium sulfite concentration in the electrolyte of the electrolytic cell is required to be 0.2 g / L; The ammonium sulfite solution adding method in the electrolysis process: a small peristaltic pump is used to add ammonium sulfite solution at the inlet of the electrolytic cell manganese sulfate electrolyte, the ammonium sulfite solution adding speed is 0.765 L / h, the ammonium sulfite concentration in the electrolyte is ensured to be 0.2±0.01 g / L, the prepared high purity manganese purity is ≥99.96%, the high purity manganese surface is smooth without burr, which meets the requirements of DJMnA brand 3N metal manganese in YB / T051-2023 industry standard.

[0025] The detection results of 3N electrolytic manganese are as follows: Test item Fe Si Se C S P Mn Industry standard ≤ 60 ppm ≤ 20 ppm ≤ 3 ppm ≤ 100 ppm ≤ 300 ppm ≤ 10 ppm ≥99.90% 3N metal manganese 50 2 ≤1 95 246 ≤1 99.96 The application relates to a 3N electrolytic manganese metal additive adding system, a 3N electrolytic manganese metal additive adding system for controlling the addition of an ammonium sulfite solution in a 3N electrolytic manganese metal additive adding method, the 3N electrolytic manganese metal additive adding system comprising a control end and an electrolytic cell 1, the electrolytic cell 1 being provided with an inlet pipeline 5 and an outlet pipeline 14, the inlet pipeline 5 and the outlet pipeline 14 being communicated and being provided with a circulating pump 15 for liquid circulation, the inlet pipeline 5 being communicated with a liquid distribution pipe 2 arranged in the electrolytic cell 1 through a water distributor 3, the outlet pipeline 14 being communicated with a liquid return pipe 11 arranged in the electrolytic cell 1 through a water collector 12, the outlet pipeline 14 being provided with an additive adding system, and an inlet valve 4 being further arranged between the inlet pipeline 5 and the water distributor 3 for controlling the flow rate, the patent mainly adopts the inorganic additive ammonium sulfite containing sulfur to completely replace selenium dioxide for an electrolytic system, and 3N electrolytic manganese metal is prepared, so that the purity of the electrolytic manganese metal is improved, neutral liquid after acid dissolution, impurity removal, filtration and purification of manganese carbonate ore powder from Ghana is added with appropriate ammonium sulfite, and then is directly introduced into an electrolytic system for electrolysis, due to the instability of the ammonium sulfite, part of the ammonium sulfite reacts in the neutral liquid, the ammonium sulfite content greatly deviates from the theoretical value, the electrolytic cell condition is unstable, and the manganese sheet purity is not high, the ammonium sulfite adding method is improved, the adding mode of the ammonium sulfite is changed into uniform distribution at the inlet port of the electrolytic cell, then the ammonium sulfite aqueous solution is added dropwise, the liquid is uniformly sent into the electrolytic cell in the mode of the liquid distribution pipe 2, the liquid circulation of the electrolytic cell is accelerated, mixing is accelerated, the electrolytic cell liquid is kept uniform, the water collector 12 keeps the liquid inlet of the liquid return pipe 11 uniform, the ammonium sulfite aqueous solution concentration and the liquid inlet speed are controlled, the ammonium sulfite content in the electrolytic cell is stabilized, the electrolytic cell condition is stable, the additive adding amount is reduced, so that the introduction of impurities is avoided, meanwhile, the oxidation-reduction reaction of the ammonium sulfite in the liquid due to the too long residence time is reduced, and finally the purity of the 3N electrolytic manganese metal is improved, and the manganese content reaches 99.97%.

[0026] In a preferred embodiment, the additive adding system mainly comprises an outlet pipeline 14 and an additive tank 16, the outlet pipeline 14 is provided with the additive tank 16 through a liquid adding pipeline 18, a peristaltic pump 17 is arranged on the liquid adding pipeline 18, the peristaltic pump 17 uniformly adds the additive into the outlet pipeline 14 through the liquid adding pipeline 18, the peristaltic pump 17 adds the ammonium sulfite solution dropwise, the ammonium sulfite liquid inlet speed is 0.5-2 L / h, the ammonium sulfite concentration in the tank liquid is ensured to be 0.1-0.2 g / L, a one-way valve is arranged on the liquid adding pipeline 18 to prevent the fluid in the outlet pipeline 14 from flowing to the liquid adding pipeline 18, and the additive tank 16 is provided with a liquid level meter.

[0027] In a preferred embodiment, the output end of the liquid outlet pipeline 14 is communicated with the circulating pipeline 6 and the buffer tank 8 through a three-way valve 9, the top of the buffer tank 8 is provided with a constant pressure pipeline 10 through which the gas flow can freely enter and exit, the circulating pipeline 6 is communicated with the liquid inlet pipeline 5, the liquid outlet end of the buffer tank 8 is communicated with the liquid inlet pipeline 5 through a variable frequency liquid pump 7 and a liquid return pipeline 20, the liquid return pipeline 20 and the circulating pipeline 6 are both provided with a one-way valve, the inside of the buffer tank 8 is provided with a partition layer 19 which divides the buffer tank 8 into two chambers, the top chamber is a fusion chamber and the bottom chamber is a liquid discharge chamber, the bottom of the partition layer 19 is provided with a neck pipe, the three-way valve 9 can selectively make the circulating electrolytic tank liquid enter the circulating pipeline 6 or the buffer tank 8 by switching, when the additive adding system is not working or the concentration of ammonium sulfite in the tank liquid is in a controllable range, the circulating electrolytic tank liquid can be selectively made to enter the circulating pipeline 6, when the concentration of ammonium sulfite in the tank liquid approaches the peak or valley value in the range, the circulating electrolytic tank liquid can be selectively made to enter the buffer tank 8, so as to avoid that the concentration of ammonium sulfite in the tank liquid breaks through the critical value, by changing the working efficiency of the circulating pump 15 and the peristaltic pump 17, the ammonium sulfite liquid inlet speed is adjusted to 0.5-2 L / h, so that the concentration of ammonium sulfite reaches the range value, and then the ammonium sulfite is sent back to the electrolytic tank 1 through the liquid return pipeline 20, so as to realize the buffering and improve the controllability of the concentration of ammonium sulfite, the buffer tank 8 is divided into two chambers by the partition layer 19, the tank liquid in the fusion chamber is mixed, after the tank liquid in the liquid discharge chamber is discharged, the tank liquid in the fusion chamber automatically enters the liquid discharge chamber.

[0028] In a preferred embodiment, the liquid outlet pipeline 14 is provided with an ammonium sulfate concentration on-line detector 13, the ammonium sulfate concentration on-line detector 13 is electrically connected with a control end, 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 on-line detector 13, so as to realize an automatic control scheme and meet the modern production requirements, the application changes the adding method of ammonium sulfite from adding in the neutral liquid tank of manganese sulfate to dropping the ammonium sulfite aqueous solution at the liquid inlet port of the electrolytic tank, controls the concentration and liquid inlet speed of the ammonium sulfite aqueous solution, realizes the stability of the ammonium sulfite content in the electrolytic tank, the stability of the electrolytic tank condition, reduces the adding amount of the additive and avoids the introduction of impurities, simultaneously reduces the oxidation and reduction reaction of ammonium sulfite due to the long residence time of ammonium sulfite in the liquid, through the change of the adding method, the purpose that the stable ammonium sulfite content in the tank liquid can be realized by adding a small amount of ammonium sulfite is realized, so as to reduce the amount of the additive, improve the purity of 3N electrolytic manganese and realize that the ammonium sulfite completely replaces the selenium dioxide for the production of 3N manganese metal in the electrolytic system.

[0029] It should be noted that all the above embodiments belong to the same inventive concept, the description of each embodiment has its own emphasis, and the description which is not described in detail in individual embodiments can be referred to the description in other embodiments.

[0030] The above embodiments only express the implementation of the present application, and the description is more specific and detailed, but it cannot be understood as a limitation on the scope of the patent. It should be noted that for ordinary skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of the present application. Therefore, the scope of protection of the present application patent should be subject to the appended claims.

Claims

1. A method of adding an additive to 3N electrolytic manganese metal, characterized by, It comprises the following steps: S1: preparation of neutral manganese sulfate solution, after acid dissolution of manganese carbonate ore powder, impurity removal and acid recovery of manganese sulfate solution are carried out by adding sodium formate and barium sulfide purifying agent, then air blowing is carried out to remove iron, and the filtered manganese sulfate solution is neutralized by ammonia water to adjust the pH value of the solution to prepare qualified manganese sulfate electrolyte; S2: preparation of ammonium sulfite additive, industrial grade ammonium sulfite is used, the sulfite content is 85%, ammonium sulfite is mixed with pure water to prepare ammonium sulfite aqueous solution; the prepared ammonium sulfite solution is adjusted to pH by ammonia water at room temperature to precipitate iron impurities in the solution, then filtered, and the filtered ammonium sulfite aqueous solution is used as electrolytic additive; S3: metal manganese electrolysis, 3N electrolytic metal manganese is prepared by diaphragm bag electrolysis, the ammonium sulfite solution is added by a small peristaltic pump at the inlet of the electrolytic cell to control the ammonium sulfite solution drop adding speed and ensure the ammonium sulfite concentration in the solution, and high-purity manganese is prepared, which has smooth surface and no burr.

2. The method of claim 1, wherein the additive is added to the 3N electrolytic manganese metal in an amount of 0.1 to 0.5 parts by weight per 100 parts by weight of the 3N electrolytic manganese metal. In the S1, the purifying agent removes impurities and recovers acid from the manganese sulfate solution, the pH value is controlled at 6.0-6.5, the pH value of the electrolytic solution is controlled in the range of 6.7-7.5, the concentration of Mn 2+ in the solution is required to be 25.00-40.00 g / L, the concentration of ammonium sulfate is required to be 80.00 g / L-110.00 g / L, and the impurity content is required to be less than 1 mg / L, including zinc, cobalt, nickel, iron, copper, chromium, lead, selenium and silicon, the potassium content is less than 15 mg / L, the sodium content is less than 4 g / L, the calcium content is less than 1 g / L, and the magnesium content is less than 25 g / L.

3. The method of claim 1, wherein the additive is added to the 3N electrolytic manganese metal in an amount of 0.1 to 0.5 parts by weight per 100 parts by weight of the 3N electrolytic manganese metal. In the S2, 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 by ammonia water at room temperature to precipitate iron impurities in the solution, then filtered, and the filtered ammonium sulfite aqueous solution is used as electrolytic additive.

4. The method of claim 1, wherein the additive is added to the 3N electrolytic manganese metal in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight of the 3N electrolytic manganese metal. In the S3, the pH value of the electrolytic cell solution is 7.0-8.0; The current density is 250-350 A / m2, the electrolytic cell solution temperature is 30.0-40.0℃, the electrolytic cell manganese is 10.0-15.0 g / L, the ammonium sulfite concentration in the electrolytic cell solution is required to be 0.1-0.2 g / L, the ammonium sulfite liquid feeding speed is 0.5-2 L / h, the ammonium sulfite concentration in the solution is ensured to be 0.1-0.2 g / L, and the prepared high-purity manganese purity is ≥99.97%.

5. A 3N EMM additive adding system comprising a 3N EMM additive adding system for controlling the addition of an ammonium sulfite solution in a 3N EMM additive adding method, the 3N EMM additive adding system comprising a control terminal and an electrolytic cell (1), the electrolytic cell (1) being provided with a liquid inlet pipeline (5) and a liquid outlet pipeline (14), the liquid inlet pipeline (5) and the liquid outlet pipeline (14) being in communication and a circulating pump (15) being installed to perform liquid circulation, characterized in that, The liquid inlet pipeline (5) is connected with the liquid distribution pipe (2) arranged in the electrolytic cell (1) through the water distributor (3), the liquid outlet pipeline (14) is connected with the liquid return pipe (11) arranged in the electrolytic cell (1) through the water collector (12), and the additive adding system is arranged on the liquid outlet pipeline (14).

6. The 3N electrolytic manganese metal additive addition system according to claim 5, characterized in that, The additive adding system mainly comprises the liquid outlet pipeline (14) and the additive tank (16), the additive tank (16) is installed on the liquid outlet pipeline (14) through the liquid adding pipeline (18), and the peristaltic pump (17) is installed on the liquid adding pipeline (18).

7. The 3N electrolytic manganese metal additive addition system according to claim 6, characterized in that, The one-way valve is arranged on the liquid adding pipeline (18) to prevent the fluid in the liquid outlet pipeline (14) from flowing to the liquid adding pipeline (18), and the liquid level meter is arranged on the additive tank (16).

8. The 3N electrolytic manganese metal additive addition system according to claim 6 or 7, characterized in that, The output end of the liquid outlet pipeline (14) is communicated with the circulating pipeline (6) and the buffer tank (8) through a three-way valve (9), the circulating pipeline (6) is communicated with the liquid inlet pipeline (5), the liquid outlet end of the buffer tank (8) is communicated with the liquid inlet pipeline (5) through a variable frequency liquid pump (7) and a liquid return pipeline (20), and the liquid return pipeline (20) and the circulating pipeline (6) are both provided with a one-way valve.

9. The 3N electrolytic manganese metal additive addition system according to claim 8, characterized in that, The buffer tank (8) is internally provided with a partition layer (19), the partition layer (19) divides the buffer tank (8) into two chambers in upper and lower positions, the top chamber is a fusion chamber, the bottom chamber is a liquid discharge chamber, and the bottom of the partition layer (19) is provided with a neck pipe.

10. The 3N electrolytic manganese metal additive addition system according to claim 8, characterized in that, An ammonium sulfate concentration on-line detector (13) is mounted on the liquid outlet pipeline (14), the ammonium sulfate concentration on-line detector (13) is electrically connected with a control end, and 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 on-line detector (13).

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