Production line for preparing manganese sulfate from zinc smelting manganese-containing slag

Abstract

The utility model discloses a production line for preparing manganese sulfate from zinc smelting manganese-containing slag, the production line for preparing manganese sulfate from zinc smelting manganese-containing slag comprises an autoclave evaporator and at least one reaction tank, the autoclave is provided with a gas inlet and a gas outlet opposite to the gas inlet, the autoclave is suitable for accommodating a zinc anode slime mixture, the gas inlet is suitable for introducing reducing gas, and the gas outlet is suitable for introducing reducing gas; carrying out reduction leaching reaction with a zinc anode mud mixture; the reaction tank is positioned at the downstream of the high-pressure kettle and is used for performing impurity removal treatment on a solution flowing into the reaction tank; and the evaporator is positioned at the downstream of the reaction tank and is suitable for evaporating, crystallizing and drying the solution flowing into the evaporator. Therefore, through the cooperation of the autoclave, the reaction tank and the evaporator, a continuous production line for reduction leaching, purification and impurity removal, evaporative crystallization and drying is formed, the high value of manganese ions and the recycling of the zinc smelting manganese-containing slag can be optimized, the technological process and the production cost can be saved, and the production line is high in applicability and universality, environmentally friendly and capable of saving energy.

Description

Technical Field

[0001] The present application relates to the field of metallurgy technology, and in particular to a production line for preparing manganese sulfate from manganese-containing slag from zinc smelting. Background Art

[0002] During the core process of zinc electrolysis, a certain concentration of manganese ions is typically added to the zinc sulfate and sulfuric acid solution to release manganese ions from the anode surface and oxidize them to form manganese dioxide, which then falls into the electrolytic cell. This reduces corrosion of the lead-based silver-containing anode plates and extends their service life. Therefore, manganese-containing zinc smelting slag, consisting primarily of manganese dioxide, lead sulfate, lead dioxide, and silver compounds, has a high metal content and potential economic value. However, traditional treatment methods for manganese-containing zinc smelting slag are relatively simple and inefficient. A common practice is to return the slag directly to the leaching process for reuse, but this often results in high manganese ion concentrations in the system solution, which in turn affects the efficiency and effectiveness of subsequent zinc electrolysis. Another treatment method is to send the manganese-containing slag directly to the lead smelting system for treatment to recover elements such as lead and silver. However, this method not only has a low metal recovery rate but also often neglects the recovery of other valuable resources such as manganese ions and sulfuric acid, resulting in significant resource waste. Utility Model Content

[0003] The present application aims to solve at least one of the technical problems existing in the prior art. To this end, one object of the present application is to provide a production line for preparing manganese sulfate from zinc smelting manganese-containing slag. The production line for preparing manganese sulfate from zinc smelting manganese-containing slag comprises an autoclave, a reaction tank, and an evaporator, forming a continuous production line for reduction leaching, purification and impurity removal, evaporation crystallization, and drying. This production line can optimize the high value of manganese ions and the resource utilization of zinc smelting manganese-containing slag, thereby reducing process flow and production costs. The production line has strong applicability and versatility, and is environmentally friendly and energy-saving.

[0004] According to some embodiments of the present application, a production line for preparing manganese sulfate from zinc smelting manganese-containing slag includes: an autoclave, an evaporator, and at least one reaction tank, wherein the autoclave has an air inlet and an air outlet opposite thereto, the autoclave is suitable for accommodating a zinc anode mud mixture, the air inlet is suitable for introducing a reducing gas and performing a reduction leaching reaction with the zinc anode mud mixture; the reaction tank is located downstream of the autoclave and is connected to the autoclave, the reaction tank is used for removing impurities from the solution flowing into the reaction tank; the evaporator is located downstream of the reaction tank, and the evaporator is suitable for evaporating, crystallizing, and drying the solution flowing into the reaction tank.

[0005] According to the production line for preparing manganese sulfate from zinc smelting manganese-containing slag of the present application, an autoclave, a reaction tank, and an evaporator can be used in combination to form a continuous production process in which reduction leaching is performed in the autoclave, purification and impurity removal is performed in the reaction tank, and evaporation, crystallization, and drying are performed in the evaporator. In the process, sulfur dioxide gas is used as the reducing gas and water is used as the leaching agent, which can optimize the high value of manganese ions and the resource utilization of zinc smelting manganese-containing slag, save process flow and production costs, and the production process has strong applicability and versatility. At the same time, there is no pollution and wastewater discharge in the process, which is environmentally friendly and energy-saving.

[0006] In some embodiments, the production line for preparing manganese sulfate from zinc smelting manganese-containing slag further includes: a filtering device, wherein the filtering devices are multiple and are arranged in a one-to-one correspondence with the autoclave, the reaction tank, and the evaporator, and are used to filter the solid products of the autoclave, the reaction tank, and the evaporator.

[0007] According to some embodiments of the present application, the air inlet and the air outlet are both arranged at the top of the autoclave, and the autoclave also has a feed port and a discharge port. The feed port is arranged at the top of the autoclave, and its projection in the height direction of the autoclave is located between the air inlet and the air outlet, and the discharge port is arranged at the bottom of the autoclave.

[0008] Furthermore, a pump body is provided between the discharge port of the autoclave and the reaction tank.

[0009] In some embodiments, the production line for preparing manganese sulfate from zinc smelting manganese-containing slag further includes: a pretreatment device, which is suitable for storing zinc smelting manganese-containing slag and obtaining zinc anode mud by water washing, and the pretreatment device is located upstream of the autoclave and is connected to the autoclave.

[0010] According to some embodiments of the present application, the reaction tank includes: a first reaction tank, a first feed port of the first reaction tank is connected to a feed port of the autoclave, the first reaction tank is suitable for placing a potassium and sodium removal reagent to convert the potassium and sodium elements in the solution therein into solid products, and a conveyor belt is provided at one end of the first reaction tank, and the conveyor belt is suitable for conveying the potassium and sodium removal reagent to the first reaction tank.

[0011] Furthermore, the reaction tank also includes: a second reaction tank, the second inlet of the second reaction tank is connected to the first outlet of the first reaction tank, and the second reaction tank is suitable for placing an iron removal reagent to convert the iron element in the solution therein into a solid product.

[0012] Furthermore, the reaction tank also includes: a third reaction tank, the third feed port of the third reaction tank is connected to the second discharge port of the second reaction tank, and the third reaction tank is suitable for placing a heavy metal removal reagent to convert the heavy metal elements in the solution therein into solid products.

[0013] Furthermore, the reaction tank also includes: a fourth reaction tank, the fourth feed port of the fourth reaction tank is connected to the third discharge port of the third reaction tank, and the fourth reaction tank is suitable for placing a calcium and magnesium removal reagent to convert the calcium and magnesium elements in the solution therein into solid products.

[0014] According to some embodiments of the present application, the production line for preparing manganese sulfate from zinc smelting manganese-containing slag further includes: a pressure detection component and a temperature detection component, wherein the pressure detection component is arranged in the autoclave and is suitable for detecting the pressure of the gas in the autoclave; the temperature detection component is constructed in multiple parts and is respectively arranged in the autoclave, the reaction tank and the evaporator to respectively detect the temperatures in the autoclave, the reaction tank and the evaporator.

[0015] Additional aspects and advantages of the present application will be given in part in the description below, and in part will become obvious from the description below, or will be learned through practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The above and / or additional aspects and advantages of the present application will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, in which:

[0017] Figure 1 is a diagram of a production line for preparing manganese sulfate from zinc smelting manganese-containing slag according to some embodiments of the present application;

[0018] Figure 2 This is a process flow chart of a production line for preparing manganese sulfate from zinc smelting manganese-containing slag according to some embodiments of the present application.

[0019] Reference numerals:

[0020] 10. Autoclave; 10a. Air inlet; 10b. Air outlet; 10c. Cavity; 10d. Feed inlet; 101. Agitator;

[0021] 21. First reaction tank; 22. Second reaction tank; 23. Third reaction tank; 24. Fourth reaction tank; 25. Stirring rod;

[0022] 30. Evaporator;

[0023] 40. Filter device;

[0024] 50. Pump body;

[0025] 60. Conveyor belt;

[0026] 71. Pressure detection component; 72. Temperature detection component;

[0027] 81. Storage barrel; 82. Funnel;

[0028] 91. First pipe section; 92. Second pipe section; 93. Third pipe section; 94. Fourth pipe section. DETAILED DESCRIPTION

[0029] To make the purpose, technical solutions, and advantages of the embodiments of this application more clear, the technical solutions in the embodiments of this application will be clearly described below in conjunction with the drawings in the embodiments of this application. Obviously, the described embodiments are part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0030] Unless otherwise defined, all technical and scientific terms used in this application have the same meanings as commonly understood by those skilled in the art to which this application belongs. The terms used in the specification of this application are for the purpose of describing specific embodiments only and are not intended to limit this application. The terms "including" and "having" and any variations thereof in the specification and claims of this application and the above-mentioned drawings are intended to cover non-exclusive inclusions. The terms "first" and "second" in the specification and claims of this application or the above-mentioned drawings are used to distinguish different objects, rather than to describe a specific order or a primary-secondary relationship.

[0031] References to "embodiments" in this application mean that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor does it constitute an independent or alternative embodiment that is mutually exclusive of other embodiments.

[0032] In the description of this application, it should be noted that, unless otherwise expressly specified or limited, the terms "mounted," "connected," "connected," and "attached" should be understood in a broad sense. For example, they may refer to fixed connections, detachable connections, or integral connections; they may refer to direct connections, indirect connections through an intermediate medium, or internal connections between two components. Those skilled in the art will understand the specific meanings of the above terms in this application based on specific circumstances.

[0033] The term "and / or" in this application simply describes an association between related objects, indicating that three possible relationships exist. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. In addition, the character " / " in this application generally indicates that the related objects are in an "or" relationship.

[0034] In the embodiments of this application, the same reference numerals represent the same components, and for the sake of brevity, detailed descriptions of the same components in different embodiments are omitted. It should be understood that the thickness, length, width, and other dimensions of the various components in the embodiments of this application, as well as the overall thickness, length, width, and other dimensions of the integrated device shown in the drawings are merely illustrative and should not constitute any limitation on this application.

[0035] In the description of the present application, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential" and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present application.

[0036] In the description of the present application, a first feature being “on” or “under” a second feature may include the first and second features being in direct contact with each other, or the first and second features being in contact with each other not directly but via another feature therebetween.

[0037] In the description of this application, a first feature “on”, “above” and “above” a second feature includes the first feature being directly above and obliquely above the second feature, or simply means that the first feature is horizontally higher than the second feature.

[0038] The term "plurality" used in this application refers to two or more (including two).

[0039] Reference below Figure 1 and Figure 2 The present invention describes a production line for preparing manganese sulfate from zinc smelting manganese-containing slag according to an embodiment of the present application.

[0040] like Figure 1 As shown, according to some embodiments of the present application, a production line for preparing manganese sulfate from zinc smelting manganese-containing slag includes: an autoclave 10, an evaporator 30 and at least one reaction tank.

[0041] The autoclave 10 has an air inlet 10a and an air outlet 10b opposite thereto. The autoclave 10 is suitable for accommodating a zinc anode mud mixture. The air inlet 10a is suitable for introducing a reducing gas and performing a reduction leaching reaction with the zinc anode mud mixture. The reaction tank is located downstream of the autoclave 10 and is connected to the autoclave 10. The reaction tank is used to remove impurities from the solution flowing into it. The evaporator 30 is located downstream of the reaction tank. The evaporator 30 is suitable for evaporating, crystallizing and drying the solution flowing into it.

[0042] Specifically, the autoclave 10 may have a cavity 10c formed therein. Materials such as the zinc anode slime mixture may be contained within the cavity 10c and undergo mixing and chemical reactions therein. The autoclave 10 isolates the materials within the cavity 10c from the external environment and provides the necessary environment for the chemical reactions of the materials, thereby ensuring the safe, efficient, and accurate chemical reactions of the materials within the cavity 10c. The autoclave 10 may also be equipped with an agitator 101 or may be configured as an autoclave 10 with an agitator 101, such as a magnetic agitation autoclave 10. The agitator 101 is rotated by a magnetic coupling to achieve material mixing and reaction, thereby avoiding leakage issues associated with conventional mechanical seals and packing seals, ensuring leak-free operation under high-temperature and high-pressure conditions. The autoclave 10 has an air inlet 10a and an air outlet 10b, which can connect the cavity 10c with the outside or other accommodating cavities. The air inlet 10a is used to introduce reducing gas (such as sulfur dioxide gas) into the cavity 10c. The reducing gas is used to react with the zinc anode mud mixture, so that the manganese element in the zinc anode mud mixture can be transferred from the solid phase to the liquid phase to form a crude manganese sulfate solution, so as to achieve efficient leaching of manganese for the subsequent preparation of manganese sulfate, and the air outlet 10b can be used to discharge the tail gas after the reaction for centralized treatment and environmentally friendly discharge of the tail gas. The air inlet 10a and the air outlet 10b can be opposite to each other in the horizontal direction and spaced apart in the circumferential direction of the autoclave 10, so that the air inlet 10a and the air outlet 10b can form a direct airflow channel to optimize the airflow path, which helps to improve the smoothness of gas circulation and gas utilization in the autoclave 10; the reaction tank is located downstream of the autoclave 10 and is connected to the autoclave 10. The autoclave 10 is connected, and the crude manganese sulfate solution after reduction leaching can enter the reaction tank. Impurities contained in the crude manganese sulfate solution are removed by chemical reactions in the reaction tank, which can remove impurity elements in the solution and improve the purity of the manganese sulfate. At the same time, metals with economic value in the impurities can also be enriched and recovered. The evaporator 30 is located downstream of the reaction tank. The evaporator 30, the reaction tank and the autoclave 10 can be connected by pipelines. The evaporator 30 can be equipped with a heating device and a condensing device to control the evaporation temperature and crystallization conditions. The solution after impurity removal in the reaction tank can be sent to the evaporator 30 for evaporation, crystallization and drying. The evaporator 30 evaporates the water in the solution by heating, and the manganese sulfate is gradually concentrated and crystallized. Subsequently, the residual water in the crystals is removed by a drying step, etc., so that a battery-grade manganese sulfate product (i.e., a manganese sulfate product with high purity that meets the requirements for battery material production) can be finally obtained.

[0043] It should be noted that the aforementioned zinc anode slime mixture refers to a mixture formed by mixing zinc anode slime with water at a specific liquid-to-solid ratio. Compared to the sulfuric acid leaching method typically used in related art, the use of water as a leaching agent in this application can significantly reduce the acidity of the crude manganese sulfate solution. This not only reduces the amount of neutralizer used in subsequent processing, saving production costs, but also reduces equipment corrosion and environmental pollution. In some embodiments, the liquid-to-solid ratio of zinc anode slime to water is set within a range of 3 to 5 to achieve a good leaching effect of manganese in the zinc anode slime while reducing the acidity of the crude manganese sulfate solution.

[0044] In addition, the above-mentioned reducing gas is constructed as sulfur dioxide gas. At room temperature, sulfur dioxide can chemically react with manganese oxides in zinc anode mud, reducing them to water-soluble manganese sulfate, thereby realizing the transfer of manganese elements from the solid phase to the liquid phase. Therefore, the addition of sulfur dioxide gas allows the entire leaching process to react at room temperature, avoiding the use of harsh reaction conditions such as high temperature and high pressure, thereby reducing production energy consumption and equipment investment. In addition, this process does not introduce impurities, ensuring the purity and quality of the final product, and further saving the impurity removal steps and costs in the subsequent processing process.

[0045] According to the production line for preparing manganese sulfate from zinc smelting manganese-containing slag of the present application, a high-pressure autoclave 10, a reaction tank, and an evaporator 30 can be used to form a continuous production process in which reduction leaching is performed in the autoclave 10, purification and impurity removal is performed in the reaction tank, and evaporation, crystallization, and drying are performed in the evaporator 30. In addition, sulfur dioxide gas is used as a reducing gas and water is used as a leaching agent in the process, which can optimize the high value of manganese ions and the resource utilization of zinc smelting manganese-containing slag, save process flow and production costs, and the production process has strong applicability and versatility. At the same time, there is no pollution and wastewater discharge in the process, which is environmentally friendly and energy-saving.

[0046] like Figure 1 As shown, according to some embodiments of the present application, the production line for preparing manganese sulfate from manganese-containing slag from zinc smelting further includes: a filtering device 40, wherein the filtering devices 40 are multiple and are arranged in a one-to-one correspondence with the autoclave 10, the reaction tank and the evaporator 30, and are used to filter the solid products of the autoclave 10, the reaction tank and the evaporator 30.

[0047] Specifically, the filter device 40 can filter solid particles. The type of filter device 40 can be selected according to actual production needs, for example, it can be configured as a filter press, vacuum filter, or centrifugal filter to meet the properties and processing capacity requirements of different solid products. Multiple filter devices 40 are set up in the production line, and these filter devices 40 correspond to the autoclave 10, the reaction tank, and the evaporator 30 respectively. This ensures that the solid products generated in each production link can be promptly and effectively processed. Among them, the filter device 40 corresponding to the autoclave 10 can filter the solid product after the zinc anode mud mixture in the autoclave 10 reacts with the reducing gas (sulfur dioxide gas). After filtration, a lead-silver slag solid product and a crude manganese sulfate solution can be obtained. The filter device 40 corresponding to the reaction tank can filter impurities after purification and impurity removal in the reaction tank. After filtration, a valuable metal solid product and a manganese sulfate solution can be obtained. The filter device 40 corresponding to the evaporator 30 can filter the crystals produced by evaporation and concentration in the evaporator 30 to obtain a manganese sulfate solid product.

[0048] The filter device 40 can, on the one hand, filter out solid particles, including unreacted raw materials, impurities, and reaction precipitates. This filtration ensures a clear solution before entering the next production stage, helping to improve the purity and stability of the final manganese sulfate product. Furthermore, the filter device 40 can filter out lead and silver residues, enabling the recovery of valuable metals. Furthermore, the filter device 40 ensures the continuity and efficiency of the production line, improving production efficiency and also contributing to the purity of the final product.

[0049] like Figure 1 As shown, according to some embodiments of the present application, the air inlet 10a and the air outlet 10b are both arranged at the top of the autoclave 10. The autoclave 10 also has a feed port 10d and a discharge port. The feed port 10d is arranged at the top of the autoclave 10, and its projection in the height direction of the autoclave 10 is located between the air inlet 10a and the air outlet 10b. The discharge port is arranged at the bottom of the autoclave 10.

[0050] Specifically, the air inlet 10a and the air outlet 10b of the autoclave 10 are both located at the top of the autoclave 10 to facilitate the introduction of reducing gas and the discharge of exhaust gas after the reaction. The feed port 10d of the autoclave 10 is used for feeding. The feed port 10d is located at the top of the autoclave 10, and its projection in the height direction of the autoclave 10 is located between the air inlet 10a and the air outlet 10b. In this way, the material can smoothly enter the autoclave 10 from the top and fully contact and react with the introduced reducing gas during the reaction process, which can improve the reaction efficiency and product quality. The discharge port of the autoclave 10 is located at the bottom of the autoclave 10, which is conducive to the discharge and collection of the reaction products. Through the discharge port, the solid product and the crude solution of manganese sulfate generated after the reaction can be discharged from the autoclave 10 for subsequent separation and purification operations.

[0051] like Figure 1 As shown, according to some embodiments of the present application, a pump body 50 is provided between the discharge port of the autoclave 10 and the reaction tank.

[0052] Specifically, there is typically a certain height difference or distance between the autoclave 10 and the reaction tank, and the feed port 10d of the autoclave 10 is located at the bottom, while the feed port of the reaction tank is generally located at the top. The pump body 50 can provide the necessary conveying power, so that the material at the lower level can be pumped to the upper level. The pump body 50 can smoothly transport the material (coarse manganese sulfate solution) after the reaction in the autoclave 10 is completed to the reaction tank, thereby achieving material transportation between the autoclave 10 and the reaction tank. The pump body 50 provides more possibilities for the layout of the autoclave 10 and the reaction tank, as well as the layout of the pipeline between the autoclave 10 and the reaction tank, which can effectively improve the flexibility and application range of the production line for preparing manganese sulfate from zinc smelting manganese-containing slag. In addition, during the production process, by adjusting the speed or operating pressure of the pump body 50, the material delivery speed and flow rate can also be controlled accordingly, which is conducive to improving the continuity and stability of the production line.

[0053] In addition, in some specific embodiments of the present application, a connecting pipe is provided between the autoclave 10 and the reaction tank to connect the autoclave 10 to the reaction tank, and the connecting pipe includes a first pipe segment 91, a second pipe segment 92, a third pipe segment 93, and a fourth pipe segment 94 connected in sequence, wherein the first pipe segment 91 is connected to the bottom of the autoclave 10, and the fourth pipe segment 94 is connected to the top of the reaction tank. The first pipe segment 91 and the third pipe segment 93 are both extended in the height direction and spaced apart, and the second pipe segment 92 and the fourth pipe segment 94 are both extended in the horizontal direction and spaced apart. By providing the first pipe segment 91 to be connected to the bottom of the autoclave 10, it is conducive to the smooth discharge of the material (manganese sulfate crude solution) after the reaction in the autoclave 10 is completed. By providing the fourth pipe segment 94 to be connected to the top of the reaction tank, it is helpful to smoothly introduce the material into the reaction tank, which can protect the bottom of the reaction tank from direct impact, extend the life of the reaction tank, and save maintenance costs. The first pipe section 91 and the third pipe section 93 extend in the height direction, which can adapt to the height difference between the autoclave 10 and the reaction tank, ensuring smooth flow of materials. The second pipe section 92 and the fourth pipe section 94 extend in the horizontal direction, which helps to improve flow smoothness and improve transportation efficiency.

[0054] Furthermore, in some other specific embodiments of the present application, the pump body 50 is disposed in the second pipe section 92 to facilitate installation and maintenance of the pump body 50 .

[0055] like Figure 1 As shown, according to some embodiments of the present application, the production line for preparing manganese sulfate from zinc smelting manganese-containing slag further includes: a pretreatment device, which is suitable for storing zinc smelting manganese-containing slag and obtaining zinc anode mud by water washing, and the pretreatment device is located upstream of the autoclave 10 and is connected to the autoclave 10.

[0056] Specifically, the pretreatment device is located upstream of the autoclave 10. Zinc smelting manganese-containing slag can be pretreated by water washing within the pretreatment device to produce zinc anode slime. This water washing pretreatment can be understood as mixing the zinc smelting manganese-containing slag with water at a preset liquid-to-solid ratio, stirring at a preset temperature for a predetermined period of time, and filtering to produce zinc anode slime and wash water. Water washing removes impurities and soluble substances from the zinc smelting manganese-containing slag, resulting in relatively pure zinc anode slime, thereby improving the quality of the raw material and contributing to the purity of the final manganese sulfate product. The pretreatment device can be connected to the autoclave 10, and the zinc anode slime after water washing can be delivered to the autoclave 10 for subsequent reactions and processing.

[0057] In addition, in some specific embodiments of the present application, the liquid-to-solid ratio of zinc smelting manganese-containing slag to water is set in the range of 2 to 4, the preset time for mixing and stirring the zinc smelting manganese-containing slag and water is 0.5h, and the preset stirring temperature is set to 25°C to 40°C to achieve a good water washing pretreatment effect.

[0058] For example, the liquid-solid ratio of zinc smelting manganese-containing slag to water is 1.5:1. As shown in Example 1 in Table 1, the zinc smelting manganese-containing slag and water are mixed and washed at a liquid-solid ratio of 1.5:1. After washing, the content of the main metal manganese element in preparing manganese sulfate can be increased from 41.11% to 42.36% compared with before washing, which can increase the output of manganese sulfate. At the same time, the content of valuable metals is also increased to a certain extent. For example, the content of lead element increases from 3.68% to 4.21%, and the content of silver element increases from 0.0132% to 0.0156%, which can improve the recovery rate of valuable metals in zinc anode mud.

[0059] Table 1 Content of metal elements in manganese-containing slag from zinc smelting in Example 1 (%)

[0060] element <![CDATA[H2O]]> Mn Pb Mg Ag Zn Ca Cl K Na Fe Before washing 22.12 41.11 3.68 0.68 0.0132 1.56 0.92 0.085 1.5 0.025 0.052 After washing 22.50 42.36 4.21 0.058 0.0156 1.54 0.89 0.015 1.46 0.024 0.051

[0061] Under the conditions of Example 1, washed zinc anode slime was mixed with water at room temperature at a liquid-to-solid ratio of 3:1, added to an autoclave 10, stirred at 400 rpm in agitator 101, and sulfur dioxide gas was introduced for a 1.2-hour reaction. Filtering yielded a crude manganese sulfate solution and lead-silver slag. The crude manganese sulfate solution had a pH of 2.0, a manganese ion concentration of 157.1 g / L, 1.49 g / L zinc, 3.85 g / L potassium, 0.55 g / L calcium, 0.15 g / L magnesium, and 0.022 g / L iron. The lead-silver slag contained 27.97% lead, 0.115% silver, 0.05% zinc, 13% strontium, and 0.12% manganese, and could be sold directly, offering high economic efficiency. The crude manganese sulfate solution was subsequently purified in a reaction tank, evaporated and crystallized in an evaporator 30, and dried to yield qualified battery-grade manganese sulfate, the composition of which is shown in Table 2.

[0062] Table 2 Manganese sulfate composition (%) under the conditions of Example 1

[0063] element Mn Pb Mg Zn Ca K Na Fe Cu Cd content 31.87 0.0011 0.016 0.0013 0.02 0.01 0.01 0.0018 0.002 0.001 Qualified products 31.80 0.0015 0.02 0.002 0.02 0.01 0.01 0.002 0.002 0.001

[0064] Under the conditions of Example 1, the manganese leaching effect in the zinc anode mud is good, and the lead, silver and strontium in the slag are efficiently enriched. After the solution is purified, evaporated, crystallized and dried, qualified battery-grade manganese sulfate can be prepared.

[0065] As shown in Table 3, in Example 2, when the liquid-to-solid ratio of zinc smelting manganese-containing slag to water is 2:1, the zinc smelting manganese-containing slag and water are mixed and washed at a liquid-to-solid ratio of 2:1. After washing, the main metal manganese element in preparing manganese sulfate can be increased from 49.76% to 49.83% compared with before washing, which can achieve an increase in manganese sulfate production. At the same time, the valuable metal content is also increased to a certain extent, for example, the lead content increases from 3.59% to 4.14%, and the silver content increases from 0.0211% to 0.0236%, which can achieve an increase in the recovery rate of valuable metals in zinc anode mud.

[0066] Table 3 Content of metal elements in manganese-containing slag from zinc smelting in Example 2 (%)

[0067] element <![CDATA[H2O]]> Mn Pb Mg Ag Zn Ca Cl K Na Fe Before washing 23.51 49.76 3.59 0.072 0.0211 0.15 0.9 0.061 1.52 0.027 0.06 After washing 22.20 49.83 4.14 0.062 0.0236 0.12 0.9 0.01 1.45 0.025 0.064

[0068] Under the conditions of Example 2, washed zinc anode slime was mixed with water at room temperature in a liquid-to-solid ratio of 4:1. The mixture was then added to an autoclave 10, stirred at 400 rpm in a stirrer 101, and sulfur dioxide gas was introduced for a reaction period of 1.2 hours. Filtering yielded a crude manganese sulfate solution and a lead-silver slag. The crude manganese sulfate solution had a pH of 1.0, a manganese ion concentration of 141.7 g / L, 0.31 g / L zinc, 3.98 g / L potassium, 0.35 g / L calcium, 0.15 g / L magnesium, and 0.02 g / L iron. The lead-silver slag contained 35.72% lead, 0.1185% silver, 0.07% zinc, 12.9% strontium, and 0.84% manganese. The crude manganese sulfate solution was subsequently purified in a reaction tank, evaporated and crystallized in an evaporator 30, and dried to yield qualified battery-grade manganese sulfate. Its composition is shown in Table 4.

[0069] Table 4 Manganese sulfate composition (%) under the conditions of Example 2

[0070] element Mn Pb Mg Zn Ca K Na Fe Cu Cd content 31.81 0.0013 0.02 0.002 0.017 0.01 0.01 0.002 0.0008 0.001 Qualified products 31.80 0.0015 0.02 0.002 0.02 0.01 0.01 0.002 0.002 0.001

[0071] Under the conditions of Example 2, valuable metals in the manganese-containing slag from zinc smelting are efficiently recovered, and the main metal manganese is prepared into high value-added products.

[0072] like Figure 1 and Figure 2 As shown, according to some embodiments of the present application, the reaction tank includes: a first reaction tank 21, a first feed port of the first reaction tank 21 is connected to the discharge port of the autoclave 10, the first reaction tank 21 is suitable for placing a potassium and sodium removal reagent to convert the potassium and sodium elements in the solution therein into solid products, and a conveyor belt 60 is provided at one end of the first reaction tank 21, and the conveyor belt 60 is suitable for conveying the potassium and sodium removal reagent to the first reaction tank 21.

[0073] Specifically, the first reaction tank 21 has a first feed port, and the first feed port is connected to the discharge port of the autoclave 10, so that the crude manganese sulfate solution produced after the reduction reaction in the autoclave 10 can enter the first reaction tank 21 through the discharge port of the autoclave 10 and the first feed port of the first reaction tank 21 in sequence. A potassium and sodium removal reagent can be placed in the first reaction tank 21. The potassium and sodium removal reagent can cause the potassium and sodium elements in the crude manganese sulfate solution to undergo a chemical reaction and convert them into solid products. For example, the potassium and sodium removal reagent can be constructed as ferric sulfate. After the ferric sulfate causes the crude manganese sulfate solution to undergo a chemical reaction, yellow potassium sodium iron alum slag and yellow sodium iron alum slag can be produced. At the same time, the solution in the first reaction tank 21 is converted into an iron-containing solution, and then the solution and the solid product are separated by the filtering device 40, thereby realizing the removal of potassium and sodium elements, effectively removing potassium and sodium impurities in the manganese-containing solution, and improving the purity of subsequent manganese sulfate preparation.

[0074] It should be noted that a conveyor belt 60 is provided at one end of the reaction tank. The conveyor belt 60 can transport the potassium and sodium removal reagent from the storage barrel 81 or the preparation area to the reaction tank, thereby automating the addition of the potassium and sodium removal reagent. This improves production efficiency and operational convenience. In addition, the automated addition method of the conveyor belt 60 can also ensure accurate measurement and timely addition of the potassium and sodium removal reagent, further ensuring the stability and controllability of the production process.

[0075] like Figure 1 and Figure 2 As shown, according to some embodiments of the present application, the reaction tank also includes: a second reaction tank 22, the second inlet of the second reaction tank 22 is connected to the first outlet of the first reaction tank 21, and the second reaction tank 22 is suitable for placing an iron removal reagent to convert the iron element in the solution therein into a solid product.

[0076] Specifically, the second reaction tank 22 has a second feed port, and the second feed port is connected to the first discharge port of the first reaction tank 21, so that the iron-containing solution produced after removing the potassium and sodium elements in the first reaction tank 21 can enter the second reaction tank 22 in sequence through the first discharge port and the second feed port. An iron removal reagent can be placed in the second reaction tank 22. The iron removal reagent can cause the iron element in the solution to undergo a chemical reaction and convert it into a solid product. For example, the iron removal reagent can be constructed as manganese carbonate. After manganese carbonate causes the solution to undergo a chemical reaction, iron hydroxide slag can be produced. The solution and the solid product are then separated by the filtering device 40, thereby realizing the decontamination treatment of the iron element. Therefore, through the introduction and implementation of the second reaction tank 22, the production line can further remove the iron element in the manganese-containing solution and further improve the purity of the subsequent manganese sulfate preparation.

[0077] like Figure 1 and Figure 2As shown, according to some embodiments of the present application, the reaction tank also includes: a third reaction tank 23, the third feed port of the third reaction tank 23 is connected to the second discharge port of the second reaction tank 22, and the third reaction tank 23 is suitable for placing a heavy metal removal reagent to convert the heavy metal elements in the solution therein into solid products.

[0078] Specifically, the third reaction tank 23 has a third feed port, and the third feed port is connected to the second discharge port of the second reaction tank 22, so that the solution after the iron element is removed in the second reaction tank 22 can enter the third reaction tank 23 through the second discharge port and the third feed port in sequence. A heavy metal removal reagent can be placed in the third reaction tank 23. The heavy metal removal reagent can cause some heavy metal elements (such as copper elements) in the solution to undergo a chemical reaction and convert them into solid products. For example, the heavy metal removal reagent can be constructed as barium sulfide. After the barium sulfide causes the solution to undergo a chemical reaction, some other heavy metal elements other than the main metal (manganese) are converted into sulfide solid products. The solution is then separated from the solid product by the filtering device 40, thereby realizing the decontamination treatment of some other heavy metal elements except manganese. Therefore, through the introduction and implementation of the third reaction tank 23, the production line can further remove other heavy metal elements in the manganese-containing solution, and further improve the purity of the subsequent manganese sulfate preparation.

[0079] like Figure 1 and Figure 2 As shown, according to some embodiments of the present application, the reaction tank also includes: a fourth reaction tank 24, the fourth feed port of the fourth reaction tank 24 is connected to the third discharge port of the third reaction tank 23, and the fourth reaction tank 24 is suitable for placing a calcium and magnesium removal reagent to convert the calcium and magnesium elements in the solution therein into solid products.

[0080] Specifically, the fourth reaction tank 24 has a fourth feed port, and the fourth feed port is connected to the third discharge port of the third reaction tank 23, so that the solution after removing other heavy metal elements in the third reaction tank 23 can enter the fourth reaction tank 24 through the third discharge port and the fourth feed port in sequence. A calcium and magnesium removal reagent can be placed in the fourth reaction tank 24. The calcium and magnesium removal reagent can cause the calcium and magnesium elements in the solution to undergo a chemical reaction and convert them into solid products. For example, the calcium and magnesium removal reagent can be constructed as manganese fluoride. After manganese fluoride causes the solution to undergo a chemical reaction, the calcium and magnesium elements in the solution are converted into calcium magnesium fluoride solid products. At the same time, the solution in the fourth reaction tank 24 is formed into a manganese sulfate solution, and then the manganese sulfate solution is separated from the solid product by the filtering device 40, thereby achieving the removal of calcium and magnesium elements and obtaining a pure manganese sulfate solution for preparing manganese sulfate.

[0081] It should be pointed out that the potassium (sodium) iron alum slag produced in the purification process of the first reaction tank 21, the iron hydroxide produced in the purification process of the second reaction tank 22, the sulfide produced in the purification process of the third reaction tank 23, and the fluoride produced in the purification process of the fourth reaction tank 24 can all be disposed of by pyrolysis, without polluting the environment, and are environmentally friendly.

[0082] In addition, in some specific embodiments of the present application, a rotatable stirring rod 25 is provided in the first reaction tank 21, the second reaction tank 22, the third reaction tank 23 and the fourth reaction tank 24 to improve the mixing uniformity of the reagent and the solution and the chemical reaction efficiency, so as to optimize the decontamination efficiency and effect.

[0083] In other specific embodiments of the present application, one end of the second reaction tank 22, the third reaction tank 23 and the fourth reaction tank 24 is provided with a funnel 82, and the reagents placed in the second reaction tank 22, the third reaction tank 23 and the fourth reaction tank 24, i.e., the iron removal reagent, the heavy metal removal reagent and the calcium and magnesium removal reagent, can be respectively placed in the corresponding reaction tanks through the funnel 82. The form of using the funnel 82 for placement helps to control the amount and speed of the reagent, ensuring that the reagent can be evenly added to the reaction tank, thereby improving the reaction efficiency and effect. In addition, the use of the funnel 82 can also reduce the loss and pollution of the reagent during the placement process, ensuring the safety of the operation and the cleanliness of the environment.

[0084] like Figure 1 As shown, according to some embodiments of the present application, the production line for preparing manganese sulfate from zinc smelting manganese-containing slag further includes: a pressure detection component 71 and a temperature detection component 72.

[0085] Among them, the pressure detection component 71 is arranged in the autoclave 10 and is suitable for detecting the pressure of the gas in the autoclave 10; the temperature detection component 72 is constructed into multiple and is respectively arranged in the autoclave 10, the reaction tank and the evaporator 30 to respectively detect the temperature in the autoclave 10, the reaction tank and the evaporator 30.

[0086] Specifically, the pressure detecting element 71 can be arranged in the top area of the autoclave 10. The pressure detecting element 71 is suitable for sensing and measuring the pressure change of the gas (sulfur dioxide) in the autoclave 10, and it can convert the pressure signal into an electrical signal and transmit it to the control system for real-time monitoring and adjustment. In this way, the pressure of the gas in the autoclave 10 can be accurately controlled to ensure that the reaction is carried out under optimal conditions, thereby improving the quality and yield of the product; the temperature detecting element 72 can be constructed in multiple numbers and respectively arranged on the autoclave 10, the reaction tank and the evaporator 30. The temperature detecting element 72 can be a high-precision temperature measuring element such as a thermistor, a thermocouple or an infrared temperature sensor. The multiple temperature detecting elements 72 can respectively sense and measure the temperature changes of the autoclave 10, the reaction tank and the evaporator 30, and convert the temperature signal into an electrical signal and transmit it to the control system for real-time monitoring and adjustment. In this way, the temperature in the autoclave 10, the reaction tank and the evaporator 30 can be controlled to ensure that the reduction leaching, purification and impurity removal, evaporation crystallization and drying operations are carried out within the appropriate temperature range, thereby improving production efficiency and product quality.

[0087] By introducing the pressure detection element 71 and the temperature detection element 72, the production line for preparing manganese sulfate from manganese-containing slag from zinc smelting can achieve real-time monitoring and control of the pressure and temperature inside the autoclave 10, the reaction tank, and the evaporator 30, which helps to ensure that the reaction is carried out under optimal conditions, improve the quality and output of the product, and at the same time, promptly detect and deal with potential faults or abnormal situations, thereby improving the stability and safety of the production line.

[0088] In some specific embodiments of the present application, in the autoclave 10 step, the sulfur dioxide partial pressure in the autoclave 10 is maintained at 0.1 MPa, the reduction leaching reaction time in the autoclave 10 is controlled within the range of 1 to 1.2 hours, the temperature range is set to 25°C to 50°C, and the stirring speed of the agitator 101 is set to 400 r / min to ensure good reduction leaching efficiency and effect. In some embodiments, the manganese ion concentration in the crude manganese sulfate solution after reduction leaching in the autoclave 10 is 140 to 160 g / L.

[0089] In other specific embodiments of the present application, in the reaction tank link, the first reaction tank 21 adds ferric sulfate (dosage coefficient 1.1-1.5) to adjust the pH of the solution to 2.5, and continues to react for 1.5-2 hours at a temperature of 90°C, and filters to obtain yellow jarosite slag, yellow sodium jarosite slag and an iron-containing solution; the second reaction tank 22 adds manganese carbonate (dosage coefficient 1.2-1.5) to adjust the pH of the iron-containing solution to 5.2-5.4, controls the temperature to 80°C, reacts for 1.5-2 hours, and filters to obtain iron hydroxide slag and a filtrate; the third reaction tank 23 adds barium sulfide (dosage coefficient 2.5-3.0), and mixes the reaction with the filtrate produced after the reaction in the second reaction tank 22 for 2-3 hours at a temperature of 80°C, and filters to obtain a filter residue and a filtrate; the fourth reaction tank 24 adds manganese fluoride (dosage coefficient 1.5-2.0) to the filtrate produced after the reaction in the third reaction tank 23, reacts for 1.5 hours at a temperature of 80°C, and filters to obtain a filter residue and a manganese sulfate solution.

[0090] In some other specific embodiments of the present application, in the evaporator 30, the evaporation and crystallization process of the manganese sulfate solution is as follows: the manganese sulfate solution produced after the reaction in the fourth reaction tank 24 is evaporated, concentrated and crystallized at a temperature of 90° C. to 95° C., and when the solution is about to be evaporated to dryness, it is filtered while hot to obtain a manganese sulfate mother liquor and manganese sulfate monohydrate crystals. The manganese sulfate monohydrate crystals are placed at a temperature of 120° C. and dried for 2 hours to obtain battery-grade manganese sulfate qualified products.

[0091] Throughout this specification, reference to terms such as "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples" means that the specific features, structures, materials, or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0092] Although the embodiments of the present application have been shown and described, those skilled in the art will appreciate that various changes, modifications, substitutions, and variations may be made to the embodiments without departing from the principles and intent of the present application, and that the scope of the present application is defined by the claims and their equivalents.

Claims

1. A production line for preparing manganese sulfate from manganese-containing zinc smelting slag, characterized in that: include: An autoclave (10), the autoclave (10) having an air inlet (10a) and an air outlet (10b) opposite thereto, the autoclave (10) being suitable for accommodating a zinc anode mud mixture, the air inlet (10a) being suitable for introducing a reducing gas and performing a reduction leaching reaction with the zinc anode mud mixture; at least one reaction tank, the reaction tank being located downstream of the autoclave (10) and in communication with the autoclave (10), the reaction tank being used for removing impurities from the solution flowing into the reaction tank; An evaporator (30) is located downstream of the reaction tank, and the evaporator (30) is suitable for evaporating, crystallizing and drying the solution flowing into the evaporator.

2. The production line for preparing manganese sulfate from zinc smelting manganese-containing slag according to claim 1, characterized in that: Also includes: A filtering device (40), wherein the filtering device (40) is provided in a plurality and is arranged in a one-to-one correspondence with the autoclave (10), the reaction tank, and the evaporator (30), and is used to filter the solid products in the autoclave (10), the reaction tank, and the evaporator (30).

3. The production line for preparing manganese sulfate from zinc smelting manganese-containing slag according to claim 1, characterized in that: The air inlet (10a) and the air outlet (10b) are both arranged at the top of the autoclave (10). The autoclave (10) also has a feed inlet (10d) and a discharge port. The feed inlet (10d) is arranged at the top of the autoclave (10), and its projection in the height direction of the autoclave (10) is located between the air inlet (10a) and the air outlet (10b). The discharge port is arranged at the bottom of the autoclave (10).

4. The production line for preparing manganese sulfate from zinc smelting manganese-containing slag according to claim 3, characterized in that: A pump body (50) is provided between the discharge port of the autoclave (10) and the reaction tank.

5. The production line for preparing manganese sulfate from zinc smelting manganese-containing slag according to claim 1, characterized in that: Also includes: A pretreatment device is provided, wherein the pretreatment device is suitable for storing manganese-containing slag from zinc smelting and obtaining zinc anode mud by water washing. The pretreatment device is located upstream of the autoclave (10) and is in communication with the autoclave (10).

6. The production line for preparing manganese sulfate from zinc smelting manganese-containing slag according to claim 1, characterized in that: The reaction tank comprises: a first reaction tank (21), a first material inlet of the first reaction tank (21) is connected to a material outlet of the autoclave (10), a potassium and sodium removal reagent is suitable for being placed in the first reaction tank (21) to convert potassium and sodium elements in the solution therein into solid products, and a conveyor belt (60) is provided at one end of the first reaction tank (21), and the conveyor belt (60) is suitable for conveying the potassium and sodium removal reagent to the first reaction tank (21).

7. The production line for preparing manganese sulfate from zinc smelting manganese-containing slag according to claim 6, characterized in that: The reaction tank further comprises: a second reaction tank (22), wherein a second feed port of the second reaction tank (22) is connected to a first discharge port of the first reaction tank (21), and the second reaction tank (22) is suitable for placing an iron removal reagent to convert the iron element in the solution therein into a solid product.

8. The production line for preparing manganese sulfate from zinc smelting manganese-containing slag according to claim 7, characterized in that: Also includes: A third reaction tank (23), wherein the third feed port of the third reaction tank (23) is connected to the second discharge port of the second reaction tank (22), and the third reaction tank (23) is suitable for placing a heavy metal removal reagent to convert heavy metal elements in the solution therein into solid products.

9. The production line for preparing manganese sulfate from zinc smelting manganese-containing slag according to claim 8, characterized in that: Also includes: A fourth reaction tank (24), wherein the fourth feed port of the fourth reaction tank (24) is connected to the third discharge port of the third reaction tank (23), and the fourth reaction tank (24) is suitable for placing a calcium and magnesium removal reagent to convert the calcium and magnesium elements in the solution therein into solid products.

10. The production line for preparing manganese sulfate from zinc smelting manganese-containing slag according to claim 1, characterized in that: Also includes: a pressure detection member (71), the pressure detection member (71) being disposed on the autoclave (10) and being adapted to detect the pressure of the gas in the autoclave (10); A temperature detecting element (72) is constructed in plurality and is respectively arranged in the autoclave (10), the reaction tank, and the evaporator (30) to respectively detect the temperatures in the autoclave (10), the reaction tank, and the evaporator (30).

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