Electrolytic manganese plate pre-electrolysis-plate replacement collaborative treatment process and production system thereof

Abstract

The present application relates to a kind of electrolytic manganese plate pre-electrolysis-pole replacement collaborative treatment process, after stripping manganese washing, cathode plate is sent into pre-electrolysis tank pre-electrolysis;Pre-electrolysis tank is equipped with pre-electrolyte, when pre-electrolysis, the concentration of selenious acid ion in pre-electrolyte, the concentration of selenious acid ion, the electrolytic temperature of pre-electrolyte, the pH of pre-electrolyte, manganese ion concentration;After processing, cathode plate is removed from pre-electrolysis tank, and is sent to main electrolysis tank and is electrolytic deposition, main electrolysis tank is equipped with main electrolyte, and when electrolytic deposition, the electrolytic temperature of main electrolyte, manganese ion concentration, pH is controlled, and is repeatedly.The present application also discloses a kind of electrolytic manganese plate pre-electrolysis-pole replacement collaborative treatment process with electrolytic manganese production system.In the present application, the "manual adjustment warehouse" link in main tank can be completely cancelled, the edge effect of pole plate and the uneven current density caused by frequent current rise and fall are avoided, and the risk of burst plate caused thereby is fundamentally eliminated.

Description

Technical Field

[0001] This invention belongs to the field of electrolytic manganese production, and particularly relates to a pre-electrolysis-plate replacement synergistic treatment process and production system for electrolytic manganese plates. Background Technology

[0002] Electrolytic manganese production uses a modular electrolytic cell array. After completing one electrolysis cycle, the electrode plate (cathode plate) needs to be removed from the electrolytic cell (lower plate), the attached metallic manganese is peeled off (manganese stripping), and after inspection and cleaning, it is put back into the electrolytic cell (upper plate) for the next round of electrolysis.

[0003] In the industrial production of electrolytic manganese, a process is commonly used where a stainless steel cathode plate is electrically deposited into a manganese layer within an electrolytic cell. However, in actual production, newly manufactured cathode plates or those returned to the cell after manganese stripping and cleaning lack a dense manganese seed layer on their surface and cannot directly withstand the high current density of the main electrolysis stage. Therefore, industry practice dictates that the first two hours after the cathode plate is inserted into the main electrolytic cell are considered the "pre-electrolysis / stocking period."

[0004] However, this model of forcibly embedding the pre-electrolysis process into the main electrolysis process has inherent process conflicts and technical contradictions.

[0005] First, the same main electrolytic cell is forced to implement two completely different process regimes. During the adjustment period, in order to promote the slow formation of seed crystals on the electrode surface, the current density needs to be temporarily reduced to a low level (pre-electrolysis mode); once the manganese on the electrode is normal, the current needs to be immediately increased to full load (main electrolysis mode). This frequent switching of operating conditions (from "low" to "high") within the same physical space and in a short period of time causes drastic fluctuations in cell voltage, current distribution, and electrolyte flow field. This fluctuation not only fails to provide a stable deposition environment for the newly formed manganese layer, but also easily causes uneven current density between the edge and center of the electrode, leading to stress concentration in the manganese layer and localized plate bursting. This is the underlying reason for the high plate bursting rate in existing technologies.

[0006] Secondly, the ambiguity of the adjustment operation stems from the lack of an independent quantitative environment. In existing technologies, the adjustment process relies heavily on manual experience. Operators need to patrol and inspect the main electrolytic cell, visually assessing the manganese level on the plates and deciding whether to replenish the electrolyte, add selenium dioxide (SeO2), or adjust the current. The parameters are ambiguous because the main electrolytic cell is in a non-steady state of "semi-production, semi-debugging," making it impossible to establish a precise control model like in steady-state production. Even if detection equipment is introduced, the sheer number of main electrolytic cell arrays (often hundreds) and the varying adjustment progress of each cell make it impractical to configure a detection and control system for each cell that can quickly respond to pre-electrolysis needs. This would lead to an exponential increase in equipment investment, and the control signals between cells would interfere with each other.

[0007] Secondly, disturbances during the rebalancing period can contaminate the main electrolysis system. To salvage electrodes with poor manganese loading, operators often frequently add selenium dioxide to the main electrolytic cell and repeatedly adjust the water temperature and current. This "emergency" operation disrupts the originally stable chemical balance of the main electrolytic cell, causing fluctuations in the composition of the solution, which in turn affects normal electrodes in the same or adjacent cells, resulting in a chain reaction of reagent waste and overall quality decline.

[0008] Finally, the oxide layer and impurities on the electrode surface cannot be effectively treated during low-current pre-electrolysis. Because the main electrolytic cell must also consider production capacity, the adjustment time is compressed to 1-2 hours. The passivation film on the electrode surface does not have enough time to be fully activated, and impurity ions are not effectively shielded. This results in poor manganese loading after the electrode enters the main electrolysis, necessitating an extension of the adjustment time, creating a vicious cycle.

[0009] In summary, the pain points of existing technologies, such as "cumbersome manual cell adjustment, ambiguous pre-electrolysis parameters, and high plate bursting rate," are not rooted in the operator's skill level, but rather in the systemic defects caused by forcibly coupling the disparate pre-electrolysis process with the main electrolysis process within the same electrolytic cell. Therefore, a solution is urgently needed that can physically separate the pre-electrolysis process from the main electrolytic cell and establish an independent, quantitative control system. Summary of the Invention

[0010] The purpose of this invention is to overcome the shortcomings of the prior art and provide a synergistic process for pre-electrolysis and electrode replacement of electrolytic manganese plates.

[0011] The present invention also discloses an electrolytic manganese production system for a pre-electrolysis-plate replacement synergistic treatment process for electrolytic manganese plates.

[0012] In this invention, the main electrolytic cell only needs to maintain a single, constant high current density steady-state operation. The electrode plates have already completed low-current activation and seed growth in an independent pre-electrolytic cell, and are put into full-load operation immediately upon entering the main cell. This completely eliminates the "manual adjustment" step in the main cell, avoids the electrode plate edge effect and uneven current density caused by frequent current increases and decreases, and fundamentally eliminates the risk of plate explosion caused by these factors.

[0013] A pre-electrolysis-plate replacement synergistic treatment process for electrolytic manganese plates, characterized by comprising the following steps:

[0014] (1) The cathode plate after manganese stripping and cleaning is sent into the pre-electrolysis cell for pre-electrolysis;

[0015] (2) The pre-electrolysis cell is filled with pre-electrolyte. During pre-electrolysis, the concentration of sulfite ions in the pre-electrolyte is controlled at 0.2~0.4 g / L, the concentration of selenite ions is controlled at 0.03~0.09 g / L, the electrolysis temperature of the pre-electrolyte is 36~40℃, the pH of the pre-electrolyte is 7.5~8, the concentration of manganese ions is 12~16 g / L, and the pre-electrolysis is carried out in the pre-electrolysis cell for 1~3 hours. The current in the pre-electrolysis cell is 220~260 A / m. 2 ;

[0016] (3) The cathode plate processed in step (2) is removed from the pre-electrolysis cell and transferred to the main electrolysis cell for electrolytic deposition. The main electrolysis cell is filled with the main electrolyte. During electrolytic deposition, the electrolysis temperature of the main electrolyte is controlled at 38~45℃, the manganese ion concentration is 11~14g / L, the pH is 7.0~7.5, and the A / m of the main electrolyte is 280~400A. 2 ;

[0017] (4) Repeat steps (1), (2), and (3) continuously.

[0018] Furthermore, the ratio of the number of pre-electrolytic cells to the number of main electrolytic cells is 1:9~12.

[0019] Furthermore, the pre-electrolysis cell is equipped with a concentration detection device, a current detection device, a temperature detection device, and a pH meter, and the pre-electrolysis cell is also equipped with an additive dosing device, a temperature regulating device, and a current regulating device.

[0020] Furthermore, the main electrolytic cell is equipped with a concentration detection device, a current detection device, a temperature detection device, and a pH meter, and the main electrolytic cell is equipped with an additive dosing device, a temperature regulating device, and a current regulating device.

[0021] An electrolytic manganese production system for a pre-electrolysis-plate replacement co-processing technology for electrolytic manganese plates includes a manganese stripping and cleaning unit, a pre-electrolysis cell, a main electrolysis cell, and an automatic rotating unit for transferring cathode plates between the manganese stripping and cleaning unit, the pre-electrolysis cell, and the main electrolysis cell.

[0022] The beneficial effects of this invention are:

[0023] 1. The main electrolytic cell only needs to maintain a single, constant high current density steady-state operation. The plates have already completed low-current activation and seed growth in the independent pre-electrolytic cell, and can operate at full load immediately upon entering the main cell. This completely eliminates the "manual adjustment" step in the main cell, avoids the edge effect of the plates and uneven current density caused by frequent current increases and decreases, and fundamentally eliminates the risk of plate explosion caused by this.

[0024] 2. Because the pre-electrolysis cell is independent of the large main cell array, high-precision online monitoring instruments can be configured in this cell without worrying about the cost being spread across hundreds of cells. This allows for precise quantification and control of the selenium dioxide (SeO2) addition, current density, temperature, and pH value, ensuring that each electrode plate enters the main electrolysis process in optimal condition.

[0025] 3. The pre-electrolysis cell provides a pure and controllable weak electric field environment, allowing the electrode plates to form a continuous, dense, and strongly adherent manganese seed layer during this stage. When the electrode plates are transferred to the main electrolysis cell, manganese ions grow epitaxially directly on the seed layer, solving the problems of poor manganese loading and weak bonding, and significantly improving the flatness and purity of the electrolytic manganese product. Attached Figure Description

[0026] Figure 1 This is a plan view of the present invention. Detailed Implementation

[0027] The present invention will be further described below with reference to embodiments. The following description of the embodiments is only for the purpose of helping to understand the present invention.

[0028] Example 1: A pre-electrolysis-plate replacement synergistic treatment process for electrolytic manganese plates, comprising the following steps:

[0029] (1) The cathode plate after manganese stripping and cleaning is sent into the pre-electrolysis cell for pre-electrolysis;

[0030] (2) The pre-electrolysis cell is filled with pre-electrolyte. During pre-electrolysis, the concentration of sulfite ions in the pre-electrolyte is controlled at 0.2 g / L, the concentration of selenite ions is controlled at 0.03 g / L, the electrolysis temperature of the pre-electrolyte is 36℃, the pH of the pre-electrolyte is 7.5, the concentration of manganese ions is 12 g / L, and pre-electrolysis is carried out in the pre-electrolysis cell for 1 h. The current in the pre-electrolysis cell is 220 A / m. 2 ;

[0031] (3) The cathode plate processed in step (2) is removed from the pre-electrolysis cell and transferred to the main electrolysis cell for electrolytic deposition. The main electrolysis cell is filled with the main electrolyte. During electrolytic deposition, the electrolysis temperature of the main electrolyte is controlled at 38°C, the manganese ion concentration is 11 g / L, the pH is 7.0, and the 280 A / m of the main electrolyte is controlled at 280 A / m. 2 ;

[0032] (4) Repeat steps (1), (2), and (3) continuously.

[0033] The ratio of the number of pre-electrolytic cells to the number of main electrolytic cells is 1:9~12.

[0034] The pre-electrolysis cell is equipped with a concentration detection device, a current detection device, a temperature detection device, and a pH meter. The pre-electrolysis cell is also equipped with an additive dosing device, a temperature regulation device, and a current regulation device.

[0035] The main electrolytic cell is equipped with a concentration detection device, a current detection device, a temperature detection device, and a pH meter. The main electrolytic cell is also equipped with an additive dosing device, a temperature regulation device, and a current regulation device.

[0036] Example 2: A pre-electrolysis-plate replacement synergistic treatment process for electrolytic manganese plates, comprising the following steps:

[0037] (1) The cathode plate after manganese stripping and cleaning is sent into the pre-electrolysis cell for pre-electrolysis;

[0038] (2) The pre-electrolysis cell is filled with pre-electrolyte. During pre-electrolysis, the concentration of sulfite ions in the pre-electrolyte is controlled at 0.3 g / L, the concentration of selenite ions is controlled at 0.06 g / L, the electrolysis temperature of the pre-electrolyte is 38℃, the pH of the pre-electrolyte is 7.7, the concentration of manganese ions is 14 g / L, and pre-electrolysis is carried out in the pre-electrolysis cell for 2 hours. The current in the pre-electrolysis cell is 240 A / m. 2 ;

[0039] (3) The cathode plate processed in step (2) is removed from the pre-electrolysis cell and transferred to the main electrolysis cell for electrolytic deposition. The main electrolysis cell is filled with the main electrolyte. During electrolytic deposition, the electrolysis temperature of the main electrolyte is controlled at 40℃, the manganese ion concentration is 13g / L, the pH is 7.2, and the 340A / m of the main electrolyte is controlled at 340A / m. 2 ;

[0040] (4) Repeat steps (1), (2), and (3) continuously.

[0041] The ratio of the number of pre-electrolytic cells to the number of main electrolytic cells is 1:10.

[0042] The pre-electrolysis cell is equipped with a concentration detection device, a current detection device, a temperature detection device, and a pH meter. The pre-electrolysis cell is also equipped with an additive dosing device, a temperature regulation device, and a current regulation device.

[0043] The main electrolytic cell is equipped with a concentration detection device, a current detection device, a temperature detection device, and a pH meter. The main electrolytic cell is also equipped with an additive dosing device, a temperature regulation device, and a current regulation device.

[0044] Example 3: A pre-electrolysis-plate replacement synergistic treatment process for electrolytic manganese plates, comprising the following steps:

[0045] (1) The cathode plate after manganese stripping and cleaning is sent into the pre-electrolysis cell for pre-electrolysis;

[0046] (2) The pre-electrolysis tank is filled with pre-electrolyte. During pre-electrolysis, the concentration of sulfite ions in the pre-electrolyte is controlled at 0.4 g / L, the concentration of selenite ions is controlled at 0.09 g / L, the electrolysis temperature of the pre-electrolyte is 40℃, the pH of the pre-electrolyte is 8, the concentration of manganese ions is 16 g / L, and the pre-electrolysis is carried out in the pre-electrolysis tank for 3 hours. The current in the pre-electrolysis tank is 260 A / m. 2 ;

[0047] (3) The cathode plate after step (2) is removed from the pre-electrolysis cell and transferred to the main electrolysis cell for electrolytic deposition. The main electrolysis cell is filled with the main electrolyte. During electrolytic deposition, the electrolysis temperature of the main electrolyte is controlled at 45℃, the manganese ion concentration is 14g / L, the pH is 7.5, and the 400A / m² of the main electrolyte is controlled at 400A / m². 2 ;

[0048] (4) Repeat steps (1), (2), and (3) continuously.

[0049] The ratio of the number of pre-electrolytic cells to the number of main electrolytic cells is 1:12.

[0050] The pre-electrolysis cell is equipped with a concentration detection device, a current detection device, a temperature detection device, and a pH meter. The pre-electrolysis cell is also equipped with an additive dosing device, a temperature regulation device, and a current regulation device.

[0051] The main electrolytic cell is equipped with a concentration detection device, a current detection device, a temperature detection device, and a pH meter. The main electrolytic cell is also equipped with an additive dosing device, a temperature regulation device, and a current regulation device.

[0052] Example 4: Figure 1 As shown, an electrolytic manganese production system for a pre-electrolysis-plate replacement co-processing technology for electrolytic manganese plates includes a manganese stripping and cleaning unit 1, a pre-electrolysis cell 2, a main electrolysis cell 3, and an automatic rotating unit 4 for transferring the cathode plate between the manganese stripping and cleaning unit 1, the pre-electrolysis cell 2, and the main electrolysis cell 3.

[0053] It should be noted that those skilled in the art can make various modifications to this invention without departing from its principles, and these modifications and improvements also fall within the scope of protection of the claims of this invention.

Claims

1. A pre-electrolysis-plate replacement synergistic treatment process for electrolytic manganese plates, characterized in that, Includes the following steps: (1) The cathode plate after manganese stripping and cleaning is sent into the pre-electrolysis cell for pre-electrolysis; (2) The pre-electrolysis cell is filled with pre-electrolyte. During pre-electrolysis, the concentration of sulfite ions in the pre-electrolyte is controlled at 0.2~0.4 g / L, the concentration of selenite ions is controlled at 0.03~0.09 g / L, the electrolysis temperature of the pre-electrolyte is 36~40℃, the pH of the pre-electrolyte is 7.5~8, the concentration of manganese ions is 12~16 g / L, and the pre-electrolysis is carried out in the pre-electrolysis cell for 1~3 hours. The current in the pre-electrolysis cell is 220~260 A / m. 2 ; (3) The cathode plate processed in step (2) is removed from the pre-electrolysis cell and transferred to the main electrolysis cell for electrolytic deposition. The main electrolysis cell is filled with the main electrolyte. During electrolytic deposition, the electrolysis temperature of the main electrolyte is controlled at 38~45℃, the manganese ion concentration is 11~14g / L, the pH is 7.0~7.5, and the A / m of the main electrolyte is 280~400A. 2 ; (4) Repeat steps (1), (2), and (3) continuously.

2. The pre-electrolysis-plate replacement synergistic treatment process for electrolytic manganese plates according to claim 1, characterized in that, The ratio of the number of pre-electrolytic cells to the number of main electrolytic cells is 1:9~12.

3. The pre-electrolysis-plate replacement synergistic treatment process for electrolytic manganese plates according to claim 1, characterized in that, The pre-electrolysis cell is equipped with a concentration detection device, a current detection device, a temperature detection device, and a pH meter. The pre-electrolysis cell is also equipped with an additive dosing device, a temperature regulation device, and a current regulation device.

4. The pre-electrolysis-plate replacement synergistic treatment process for electrolytic manganese plates according to claim 1, characterized in that, The main electrolytic cell is equipped with a concentration detection device, a current detection device, a temperature detection device, and a pH meter. The main electrolytic cell is also equipped with an additive dosing device, a temperature regulating device, and a current regulating device.

5. An electrolytic manganese production system for a pre-electrolysis-plate replacement synergistic treatment process for electrolytic manganese plates as described in any one of claims 1 to 4, characterized in that, It includes a manganese stripping and cleaning unit, a pre-electrolytic cell, a main electrolytic cell, and an automatic rotating unit that transfers the cathode plate between the manganese stripping and cleaning unit, the pre-electrolytic cell, and the main electrolytic cell.

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