Method for preparing electrolytic manganese by dry throwing preselection and multi-stage purification of manganese carbonate ore

Abstract

This application belongs to the field of electrolytic manganese preparation technology, specifically providing a method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification, including the following steps: a) crushing and screening the manganese carbonate ore to obtain ore of a first particle size; b) subjecting the ore of the first particle size to dry strong magnetic separation pre-selection and tailings removal to obtain pre-selected concentrate; c) grinding the pre-selected concentrate to obtain a grinding product of a second particle size; d) mixing the grinding product with water or return liquid for slurry treatment to obtain a slurry; e) mixing the slurry with sulfuric acid for chemical leaching to obtain a leaching slurry; f) subjecting the leaching slurry to multi-stage purification treatment to obtain a purified electrolyte; g) electrolyzing the purified electrolyte to obtain cathode electrolytic manganese. The electrolytic manganese obtained by this application has the advantages of high purity, low water load, and low reagent consumption.

Description

Technical Field

[0001] This application belongs to the field of electrolytic manganese preparation technology, and in particular relates to a method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification. Background Technology

[0002] Electrolytic manganese, as an important basic material in metallurgy and chemical industry, has wide and irreplaceable applications in iron and steel smelting, non-ferrous metal alloys, electronic components, and new energy battery materials. Manganese carbonate ore is an important component of global manganese resources and one of the main raw materials for producing electrolytic manganese. A typical process for producing electrolytic manganese from manganese carbonate ore usually includes crushing and grinding, pulping, sulfuric acid leaching, solution purification, electrolysis, and finished product processing.

[0003] However, with the increasing depletion of high-quality manganese ore resources, my country's manganese carbonate ore resources generally exhibit low grade and high impurity content (such as iron, calcium, magnesium, silicon, and aluminum). For such ores, if effective pre-selection and tailings removal methods are lacking in the front-end processing, a large amount of useless gangue minerals (such as quartz, calcite, and dolomite) will directly enter the subsequent hydrometallurgical system. This not only significantly increases the processing load and energy consumption of grinding, pulping, and leaching processes, but also leads to a sharp increase in sulfuric acid consumption during the leaching process, and results in a large number of impurity ions (such as Fe) being excreted. 2+ / Fe 3+ Ca 2+ Mg 2+ (etc.) enter the leachate. In the subsequent purification stage, in order to remove these impurities, a large amount of neutralizing agents, sulfiding agents and other agents need to be added, which leads to an increase in production costs and generates a large amount of difficult-to-treat waste residue, increasing environmental pressure. In addition, incomplete front-end impurity removal will also affect the purity of the electrolyte, resulting in a decrease in current efficiency and an increase in energy consumption during the electrolysis process, and ultimately affecting the purity and surface quality of the cathode manganese product.

[0004] In the prior art, there are some reports on the processing technology of manganese carbonate ore. For example, patent document CN103526018A discloses a method for processing low-manganese, high-iron manganese carbonate ore, but its technical route focuses on direct leaching and subsequent purification, with little consideration given to the physical pre-selection and tailings disposal of the ore. This results in a large amount of gangue entering the subsequent process, leading to poor overall economic efficiency. Patent document CN104018184A details the purification steps of the leachate, but its process is relatively cumbersome, and it does not fully reflect the synergistic effect between the front-end pre-selection and the subsequent step-by-step purification.

[0005] Therefore, how to reduce the amount of impurities entering the wet process system from the source and optimize the connection and synergy between leaching and purification processes to prepare high-quality electrolytic manganese from complex manganese carbonate ores at a lower cost and higher efficiency remains a technical challenge that urgently needs to be solved in this field. Summary of the Invention

[0006] To address the aforementioned issues, this application provides a method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification.

[0007] This application provides a method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification, including the following steps: a) The manganese carbonate ore is crushed and screened to obtain the first particle size ore. b) The ore of the first particle size is subjected to dry high-intensity magnetic separation pre-selection and tailings removal to obtain pre-selected concentrate; c) Grind the pre-selected concentrate to obtain a ground product of the second particle size; d) The grinding product is mixed with water or return liquid and subjected to pulping treatment to obtain a slurry; e) The slurry is mixed with sulfuric acid and chemically leached to obtain a leaching slurry; f) The leachate slurry is subjected to multi-stage purification treatment, which includes at least sequential neutralization and iron removal, sulfidation and impurity removal, and acid adjustment and oxidation processes, and solid-liquid separation is performed after each process to obtain purified electrolyte. g) Electrolyze the purified electrolyte to obtain cathode electrolytic manganese.

[0008] Furthermore, the first particle size is less than 10 mm, preferably more than 90% of which are particles smaller than 8 mm; And / or, the manganese carbonate ore has a Mn grade of 20%-32%, a SiO2 grade of 14%-22%, an Al2O3 grade of 3%-8%, an MgO grade of 6%-14%, and a CaO grade of 6%-16%.

[0009] Furthermore, the dry high-intensity magnetic separation pre-selection tailings disposal specifically includes: feeding the first-size ore into a dry roller high-intensity magnetic separator for a roughing and scavenging operation, wherein the roughing operation obtains roughing concentrate and roughing tailings, and the scavenging operation processes the roughing tailings to obtain scavenging concentrate and final tailings; the roughing concentrate and the scavenging concentrate are combined as the pre-selection concentrate.

[0010] Furthermore, the magnetic induction intensity of the coarse selection operation and / or the sweeping operation is independently 0.8T-1.2T, preferably 1.0T; And / or, the frequency of the inverter for the coarse selection operation is 30Hz-40Hz, and the frequency of the inverter for the sweep selection operation is 30Hz-40Hz. And / or, the tailings baffle of the dry roller magnetic separator has an angle of 50°-60° with the roller surface.

[0011] Furthermore, the grinding process is a two-stage ball milling process, including a first-stage ball milling and a second-stage ball milling, and the content of particles with the second particle size of -0.074mm accounts for more than 80%; And / or, the mass concentration of the slurry prepared in step d) is 30%-45%.

[0012] Furthermore, the conditions for chemical leaching in step e) are as follows: liquid-to-solid mass ratio of (4-8):1, sulfuric acid concentration of 0.6 mol / L-1.4 mol / L, leaching temperature of 40℃-90℃, and leaching time of 30 min-150 min.

[0013] Furthermore, the multi-stage purification process in step f) specifically includes: f1) Add a neutralizing agent to the leaching slurry for neutralization and iron removal treatment, and perform a first pressure filtration on the resulting slurry to obtain primary filtrate and iron removal slag; f2) Add a sulfiding agent to the primary filtrate for sulfidation and impurity removal treatment, and perform a second pressure filtration on the resulting slurry to obtain secondary filtrate and sulfidation residue; f3) Add acid and oxidant to the secondary filtrate for acid adjustment and oxidation treatment, and then perform a third pressure filtration on the resulting slurry to obtain the purified electrolyte and the oxidized purification residue.

[0014] Furthermore, in step f1), the conditions for the neutralization and iron removal treatment are: pH value controlled at 4.5-5.5, temperature at 50℃-70℃, and time at 20min-40min. And / or, in step f2), the conditions for the sulfurization impurity removal treatment are: temperature of 35℃-45℃ and time of 15min-30min; And / or, in step f3), the conditions for the acid-adjusting oxidation treatment are: temperature of 40℃-50℃ and time of 20min-40min.

[0015] Furthermore, the electrolysis conditions in step g) are: electrolysis temperature of 30℃-50℃, and cathode current density of 300A / m. 2 -400A / m 2 The electrolysis cycle is 20-30 hours.

[0016] Furthermore, it also includes step h): sequentially passivating, stripping, and packaging the cathode electrolytic manganese to obtain the electrolytic manganese product; preferably, the manganese purity of the electrolytic manganese product is not less than 99.75%.

[0017] This application provides an electrolytic manganese product, which is prepared by the method described above.

[0018] This application also provides a system for preparing electrolytic manganese from manganese carbonate ore, for implementing the above-described method, wherein the system comprises, in sequence along the material flow direction: The crushing and screening unit is used to prepare manganese carbonate ore into the first particle size. A dry magnetic separation unit is located downstream of the crushing and screening unit and is used to pre-select and remove tailings from the ore of the first particle size to obtain pre-selected concentrate. A grinding unit is located downstream of the dry magnetic separation unit and is used to finely grind the pre-selected concentrate. A slurry preparation unit, located downstream of the grinding unit, is used to prepare the grinding product into a slurry. A chemical leaching unit is located downstream of the pulping unit and is used to react the slurry with sulfuric acid to generate a leaching slurry. A multi-stage purification unit, located downstream of the chemical leaching unit, includes at least a neutralization and iron removal module connected in sequence. The system includes a chemical purification module and an acid-adjusting oxidation module, with a corresponding solid-liquid separation device installed after each module. An electrolysis unit, located downstream of the multi-stage purification unit, is used to electrolyze the purified electrolyte.

[0019] Furthermore, the dry magnetic separation unit includes at least two dry roller high-intensity magnetic separators, which are used to perform roughing and scavenging operations, respectively.

[0020] Furthermore, the grinding unit includes a first-stage ball mill and a second-stage ball mill arranged in series.

[0021] Furthermore, the multi-stage purification unit specifically includes: A neutralization and iron removal tank is used to receive the leachate slurry and carry out a neutralization reaction. The first filter press is connected downstream of the neutralization and iron removal tank; A sulfidation reaction tank is connected downstream of the liquid phase outlet of the first filter press; The second filter press is connected downstream of the vulcanization reaction tank; An acid-adjusting oxidation tank is connected downstream of the liquid phase outlet of the second filter press; The third filter press is connected downstream of the acid-adjusting oxidation tank, and its liquid phase outlet is used to output the purified electrolyte.

[0022] Furthermore, the first filter press, the second filter press, and / or the third filter press are provided with filtrate return pipelines for returning a portion of the filtrate to the upstream process.

[0023] Furthermore, the system also includes a post-processing unit located downstream of the electrolysis unit, which is used to passivate, strip, and package the cathode electrolytic manganese.

[0024] Compared with the prior art, this application has the following beneficial effects: 1. This application sets up a dry strong magnetic pre-selection process before wet treatment, which can remove some low-grade gangue minerals in advance, reduce the amount of minerals entering the subsequent pulping, chemical leaching and multi-stage purification system, thereby reducing the water load and reagent consumption of the subsequent wet treatment process. Therefore, it has good adaptability to areas with water shortage or limited water supply conditions.

[0025] 2. This application adopts a multi-stage purification process that combines chemical leaching with neutralization and iron removal, sulfidation, acid adjustment and oxidation, and multiple pressure filtration. This process can effectively convert manganese minerals in manganese carbonate ore into manganese sulfate and allow them to enter the liquid phase. At the same time, it removes iron impurities, heavy metal impurities, and other harmful impurities in the leaching solution in stages, resulting in clear purification levels. This is beneficial for improving the purity and compositional stability of the electrolyte.

[0026] 3. This application organically combines dry strong magnetic pre-selection, two-stage ball milling, chemical leaching, multi-stage purification, and electrolytic post-treatment to form a complete process flow for the direct preparation of electrolytic manganese products from manganese carbonate ore. The process is closely connected, the steps are reasonably set, and the purified electrolyte obtained can be directly entered into the electrolysis process, ultimately obtaining electrolytic manganese products with stable quality, which is suitable for industrial implementation. Attached Figure Description

[0027] Figure 1 This is a schematic diagram of the process for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification, as described in this application. Detailed Implementation

[0028] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0030] When using “including,” “having,” and “contains” as described herein, the intention is to cover non-exclusive inclusion, unless an explicit qualifying term such as “only,” “consisting of,” etc., is used, in which case another component may be added.

[0031] The terms "preferred," "more preferably," "better," and "even better" used in this application refer to embodiments of this application that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this application. That is, in this application, "preferred," "more preferably," "better," and "even better" are merely descriptions of implementations or embodiments with better effects, but do not constitute a limitation on the scope of protection of this application.

[0032] In this application, terms such as "further," "even more," and "particularly" are used for descriptive purposes and indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0033] In this application, "at least one" means one or more, such as one, two, or more. "Multiple" or "several" means at least two, such as two, three, etc., and "multi-layered" means at least two layers, such as two layers, three layers, etc., unless otherwise explicitly specified. In the description of this application, "several" means at least one, such as one, two, etc., unless otherwise explicitly specified.

[0034] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0035] Unless otherwise specified, all steps in this application may be performed sequentially or randomly. For example, the method comprising steps (a) and (b) indicates that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order; for example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc. Unless otherwise stated, singular terms may include plural forms and should not be construed as having a quantity of one.

[0036] In this application, "above" or "below" includes the number itself. For example, "below 1" includes 1.

[0037] In this application, room temperature refers to 0~40℃, including but not limited to 10~40℃, or further to 20~30℃.

[0038] Based on extensive experimental research, this application provides a method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification, comprising the following steps: a) The manganese carbonate ore is crushed and screened to obtain the first particle size ore. b) The ore of the first particle size is subjected to dry high-intensity magnetic separation pre-selection and tailings removal to obtain pre-selected concentrate; c) Grind the pre-selected concentrate to obtain a ground product of the second particle size; d) The grinding product is mixed with water or return liquid and subjected to pulping treatment to obtain a slurry; e) The slurry is mixed with sulfuric acid and chemically leached to obtain a leaching slurry; f) The leachate slurry is subjected to multi-stage purification treatment, which includes at least sequential neutralization and iron removal, sulfidation and impurity removal, and acid adjustment and oxidation processes, and solid-liquid separation is performed after each process to obtain purified electrolyte. g) Electrolyze the purified electrolyte to obtain cathode electrolytic manganese.

[0039] Furthermore, the first particle size is less than 10 mm, preferably more than 90% of which are particles smaller than 8 mm; And / or, the manganese carbonate ore has a Mn grade of 20%-32%, a SiO2 grade of 14%-22%, an Al2O3 grade of 3%-8%, an MgO grade of 6%-14%, and a CaO grade of 6%-16%.

[0040] In some specific embodiments, the manganese carbonate ore has a Mn grade of 20%-32%, for example, it can be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32% or more; a SiO2 grade of 14%-22%, for example, it can be 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22% or more; an Al2O3 grade of 3%-8%, for example, it can be 3%, 4%, 5%, 6%, 7%, 8% or more; a MgO grade of 6%-14%, for example, it can be 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or more; and a CaO grade of 6%-16%, for example, it can be 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16% or more.

[0041] Furthermore, the dry high-intensity magnetic separation pre-selection tailings disposal specifically includes: feeding the first-size ore into a dry roller high-intensity magnetic separator for a roughing and scavenging operation, wherein the roughing operation obtains roughing concentrate and roughing tailings, and the scavenging operation processes the roughing tailings to obtain scavenging concentrate and final tailings; the roughing concentrate and the scavenging concentrate are combined as the pre-selection concentrate.

[0042] Furthermore, the magnetic induction intensity of the coarse selection operation and / or the sweeping operation is independently 0.8T-1.2T, preferably 1.0T; And / or, the frequency of the inverter for the coarse selection operation is 30Hz-40Hz, and the frequency of the inverter for the sweep selection operation is 30Hz-40Hz. And / or, the tailings baffle of the dry roller magnetic separator has an angle of 50°-60° with the roller surface.

[0043] Furthermore, the grinding process is a two-stage ball milling process, including a first-stage ball milling and a second-stage ball milling, and the content of particles with the second particle size of -0.074mm accounts for more than 80%; And / or, the mass concentration of the slurry prepared in step d) is 30%-45%.

[0044] In some specific embodiments, the mass concentration of the slurry prepared in step d) is 30%-45%, for example, it can be 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45% or more. Furthermore, the conditions for chemical leaching in step e) are as follows: liquid-to-solid mass ratio of (4-8):1, sulfuric acid concentration of 0.6 mol / L-1.4 mol / L, leaching temperature of 40℃-90℃, and leaching time of 30 min-150 min.

[0045] In some specific embodiments, the liquid-to-solid mass ratio is (4-8):1, for example, it can be 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1 or any range or value thereof.

[0046] Furthermore, the multi-stage purification process in step f) specifically includes: f1) Add a neutralizing agent to the leaching slurry for neutralization and iron removal treatment, and perform a first pressure filtration on the resulting slurry to obtain primary filtrate and iron removal slag; f2) Add a sulfiding agent to the primary filtrate for sulfidation and impurity removal treatment, and perform a second pressure filtration on the resulting slurry to obtain secondary filtrate and sulfidation residue; f3) Add acid and oxidant to the secondary filtrate for acid adjustment and oxidation treatment, and then perform a third pressure filtration on the resulting slurry to obtain the purified electrolyte and the oxidized purification residue.

[0047] Furthermore, in step f1), the conditions for the neutralization and iron removal treatment are: pH value controlled at 4.5-5.5, temperature at 50℃-70℃, and time at 20min-40min. And / or, in step f2), the conditions for the sulfurization impurity removal treatment are: temperature of 35℃-45℃ and time of 15min-30min; And / or, in step f3), the conditions for the acid-adjusting oxidation treatment are: temperature of 40℃-50℃ and time of 20min-40min.

[0048] Preferably, the neutralizing agent is ammonia water, and the mass fraction of ammonia water is 10%-20%. In some specific embodiments, the mass fraction of ammonia water can be 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%.

[0049] Preferably, the sulfiding agent is a sodium sulfide solution with a Na2S mass fraction of 5%-15%. In some specific embodiments, the Na2S mass fraction can be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15%.

[0050] More preferably, the sulfiding agent is a sodium sulfide mixed solution, wherein the mass fraction of Na2S is 10%, the mass fraction of L-hydroxyproline is 5%, and the mass fraction of α-lipoic acid is 2%. By adding L-hydroxyproline and α-lipoic acid, the sulfidation and impurity removal capabilities are further enhanced, thereby improving the purity of the product.

[0051] Preferably, in the acid-adjusting oxidation treatment, the acid used is sulfuric acid, specifically a dilute sulfuric acid with a mass fraction of 10%-25%. In some specific embodiments, dilute sulfuric acid with mass fractions of 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, or 25% can be used. The oxidant used is hydrogen peroxide, with a mass fraction of 10%-30%. In some specific embodiments, the mass fraction of hydrogen peroxide can be 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, or 30%.

[0052] Furthermore, the electrolysis conditions in step g) are: electrolysis temperature of 30℃-50℃, and cathode current density of 300A / m. 2 -400A / m 2 The electrolysis cycle is 20-30 hours.

[0053] Furthermore, it also includes step h): sequentially passivating, stripping, and packaging the cathode electrolytic manganese to obtain the electrolytic manganese product; preferably, the manganese purity of the electrolytic manganese product is not less than 99.75%.

[0054] This application provides an electrolytic manganese product, which is prepared by the method described above.

[0055] This application also provides a system for preparing electrolytic manganese from manganese carbonate ore, for implementing the above-described method, wherein the system comprises, in sequence along the material flow direction: The crushing and screening unit is used to prepare manganese carbonate ore into the first particle size. A dry magnetic separation unit is located downstream of the crushing and screening unit and is used to pre-select and remove tailings from the ore of the first particle size to obtain pre-selected concentrate. A grinding unit is located downstream of the dry magnetic separation unit and is used to finely grind the pre-selected concentrate. A slurry preparation unit, located downstream of the grinding unit, is used to prepare the grinding product into a slurry. A chemical leaching unit is located downstream of the pulping unit and is used to react the slurry with sulfuric acid to generate a leaching slurry. A multi-stage purification unit, located downstream of the chemical leaching unit, includes at least a neutralization and iron removal module connected in sequence. The system includes a chemical purification module and an acid-adjusting oxidation module, with a corresponding solid-liquid separation device installed after each module. An electrolysis unit, located downstream of the multi-stage purification unit, is used to electrolyze the purified electrolyte.

[0056] Furthermore, the dry magnetic separation unit includes at least two dry roller high-intensity magnetic separators, which are used to perform roughing and scavenging operations, respectively.

[0057] Furthermore, the grinding unit includes a first-stage ball mill and a second-stage ball mill arranged in series.

[0058] Furthermore, the multi-stage purification unit specifically includes: A neutralization and iron removal tank is used to receive the leachate slurry and carry out a neutralization reaction. The first filter press is connected downstream of the neutralization and iron removal tank; A sulfidation reaction tank is connected downstream of the liquid phase outlet of the first filter press; The second filter press is connected downstream of the vulcanization reaction tank; An acid-adjusting oxidation tank is connected downstream of the liquid phase outlet of the second filter press; The third filter press is connected downstream of the acid-adjusting oxidation tank, and its liquid phase outlet is used to output the purified electrolyte.

[0059] Furthermore, the first filter press, the second filter press, and / or the third filter press are provided with filtrate return pipelines for returning a portion of the filtrate to the upstream process.

[0060] Furthermore, the system also includes a post-processing unit located downstream of the electrolysis unit, which is used to passivate, strip, and package the cathode electrolytic manganese.

[0061] The present application will be further illustrated by the following examples, but these examples do not limit the scope of the present application.

[0062] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in this application, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this application have the same meaning as commonly understood by one of ordinary skill in the art. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. All reagents or instruments whose manufacturers are not specified are conventional products that can be purchased commercially. In addition to the specific methods, equipment, and materials used in the embodiments, based on the knowledge of the prior art possessed by one of ordinary skill in the art and the description in this application, any prior art methods, equipment, and materials similar to or equivalent to those described, used, or made by the methods, equipment, and materials in the embodiments of this application may be used to implement this application.

[0063] Example 1 In this embodiment, the grade of Mn in the manganese carbonate ore is 27.28%, the grade of SiO2 is 18.64%, the grade of Al2O3 is 4.72%, the grade of MgO is 9.86%, and the grade of CaO is 10.34%.

[0064] The method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification in this embodiment includes the following steps: a) Manganese carbonate ore is fed into a crushing and screening system via a conveyor belt for crushing and screening to obtain ore with a first particle size of less than 10 mm. b) The first-size mineral particles (less than 10 mm) obtained in step a) are fed into a dry roller-type high-intensity magnetic separator for roughing. The roughing magnetic induction intensity is 1.0 T, the roughing frequency converter frequency is 40 Hz, and the angle between the baffle and the roller is 60°, yielding roughing concentrate and roughing tailings. The roughing concentrate yield is 80.62%, the Mn grade is 32.15%, and the Mn recovery rate is 95.01%. The roughing tailings are further fed into a dry roller-type high-intensity magnetic separator for scavenging. The scavenging magnetic induction intensity is 1.0 T, the scavenging frequency converter frequency is 35 Hz, and the angle between the baffle and the roller is 60°, yielding scavenging concentrate and final pre-selected tailings. The scavenging concentrate yield is 7.62%, the Mn grade is 10.63%, and the Mn recovery rate is 2.97%. The final pre-selected tailings yield is 11.76%, the Mn grade is 4.68%, and the Mn recovery rate is 2.02%. The roughing concentrate and scavenging concentrate were combined and used as pre-concentration concentrate for subsequent two-stage ball milling operations. The yield of the combined pre-concentration concentrate was 88.24%, the Mn grade was 30.28%, and the total Mn recovery rate was 97.98%. c) The pre-selected concentrate obtained in step b) is fed into a first-stage ball mill and a second-stage ball mill for grinding, so that the manganese carbonate minerals are fully dissociated to obtain a second-size grinding product that meets the requirements of subsequent pulping and chemical leaching; and the content of the -0.074mm particle size in the grinding product after the second-stage ball mill is controlled to be more than 80%. d) The grinding product obtained in step c) is fed into a pulping tank and water is added for pulping to obtain a homogeneous slurry with a slurry concentration of 35%. e) The slurry obtained in step d) is fed into a chemical reaction tank to react with sulfuric acid. The reaction liquid-solid ratio is 5:1, the sulfuric acid concentration is 0.90 mol / L, the chemical reaction temperature is 70℃, and the chemical reaction time is 90 min. This converts the manganese minerals in the manganese carbonate ore into manganese sulfate and enters the liquid phase to obtain the leaching slurry. f) The leachate obtained in step e) undergoes a multi-stage purification process, which sequentially includes neutralization and iron removal, primary pressure filtration, sulfidation, secondary pressure filtration, acid adjustment and oxidation, and tertiary pressure filtration. Specifically: First, a neutralizing agent is added to the leachate for neutralization and iron removal, adjusting the pH of the system to 4.8. The mixture is stirred at 60°C for 30 minutes to precipitate iron impurities in the leachate. Then, the resulting slurry is fed into a pressure filter for primary filtration to obtain primary filtrate and iron-removed slag. Next, a sulfiding agent is added to the primary filtrate for sulfidation at 40°C for 25 minutes to precipitate heavy metal impurities such as copper, lead, zinc, cadmium, nickel, and cobalt. The sulfided slurry is then fed into a filter press for secondary filtration to obtain secondary filtrate and sulfided slag. The secondary filtrate is then fed into an acid-adjusting oxidation tank, where sulfuric acid is added to adjust the acidity, and an oxidizing agent is added for oxidation. The acid-adjusting oxidation temperature is 45℃, and the reaction time is 30 minutes to further remove residual impurities. The neutralizing agent is ammonia water with a mass fraction of 15%; the sulfiding agent is sodium sulfide solution with a Na2S mass fraction of 10%; the acid used for acid-adjusting oxidation is sulfuric acid with a mass fraction of 20%; and the oxidizing agent is hydrogen peroxide with a mass fraction of 20%. Finally, the acid-adjusted and oxidized slurry is fed into a filter press for three rounds of filtration to obtain purified electrolyte and oxidized purified residue. The resulting purified electrolyte is then used in subsequent electrolysis operations; it is fed into an electrolytic cell for electrolysis at a temperature of 40℃ and a cathode current density of 350 A / m. 2 The cathode manganese deposition cycle is 24 hours, and cathode electrolytic manganese is obtained; h) The obtained cathode electrolytic manganese is sequentially passivated, stripped and packaged to finally obtain electrolytic manganese product with a purity of 99.80%.

[0065] Example 2 In this embodiment, the grade of Mn in the manganese carbonate ore is 22.64%, the grade of SiO2 is 19.85%, the grade of Al2O3 is 5.72%, the grade of MgO is 10.46%, and the grade of CaO is 9.38%.

[0066] The method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification in this embodiment includes the following steps: a) Manganese carbonate ore is fed into a crushing and screening system via a conveyor belt for crushing and screening to obtain ore with a first particle size of less than 10 mm. b) The first-size mineral particles (less than 10 mm) obtained in step a) are fed into a dry roller-type high-intensity magnetic separator for roughing. The roughing magnetic induction intensity is 1.0 T, the roughing frequency converter frequency is 35 Hz, and the angle between the baffle and the roller is 55°, yielding roughing concentrate and roughing tailings. The roughing concentrate yield is 70.24%, the Mn grade is 28.95%, and the Mn recovery rate is 89.82%. The roughing tailings are further fed into a dry roller-type high-intensity magnetic separator for scavenging. The scavenging magnetic induction intensity is 1.0 T, the scavenging frequency converter frequency is 30 Hz, and the angle between the baffle and the roller is 55°, yielding scavenging concentrate and final pre-selected tailings. The scavenging concentrate yield is 8.16%, the Mn grade is 14.20%, and the Mn recovery rate is 5.12%. The final pre-selected tailings yield is 21.60%, the Mn grade is 5.31%, and the Mn recovery rate is 5.06%. The roughing concentrate and scavenging concentrate were combined and used as pre-concentration concentrate for subsequent two-stage ball milling operations. The yield of the combined pre-concentration concentrate was 78.40%, the Mn grade was 27.41%, and the total Mn recovery rate was 94.94%. c) The pre-selected concentrate obtained in step b) is fed into a first-stage ball mill and a second-stage ball mill for grinding, so that the manganese carbonate minerals are fully dissociated to obtain a second-size grinding product that meets the requirements of subsequent pulping and chemical leaching; and the content of the -0.074mm particle size in the grinding product after the second-stage ball mill is controlled to be more than 81%. d) The grinding product obtained in step c) is fed into a pulping tank and water is added for pulping to obtain a homogeneous slurry with a slurry concentration of 34%. e) The slurry obtained in step d) is fed into a chemical reaction tank to react with sulfuric acid. The reaction liquid-solid ratio is 4.5:1, the sulfuric acid concentration is 0.80 mol / L, the chemical reaction temperature is 65℃, and the chemical reaction time is 75 min. This converts the manganese minerals in the manganese carbonate ore into manganese sulfate and enters the liquid phase to obtain the leaching slurry. f) The leachate obtained in step e) undergoes a multi-stage purification process, which includes neutralization and iron removal, primary pressure filtration, sulfidation, secondary pressure filtration, acid adjustment and oxidation, and tertiary pressure filtration. Specifically: First, a neutralizing agent is added to the leachate for neutralization and iron removal, adjusting the pH of the system to 4.6. The mixture is stirred at 58°C for 25 minutes to precipitate iron impurities in the leachate. Then, the resulting slurry is sent to a pressure filter for primary filtration to obtain primary filtrate and iron-removed slag. Next, a sulfiding agent is added to the primary filtrate for sulfidation at 38°C for 20 minutes to precipitate heavy metal impurities such as copper, lead, zinc, cadmium, nickel, and cobalt. The sulfided slurry is then fed into a filter press for secondary filtration to obtain secondary filtrate and sulfided slag. The secondary filtrate is then fed into an acid-adjusting oxidation tank, where sulfuric acid is added to adjust the acidity, and an oxidizing agent is added for oxidation. The acid-adjusting oxidation temperature is 42℃, and the reaction time is 25 minutes to further remove residual impurities. The neutralizing agent is ammonia water with a mass fraction of 15%; the sulfiding agent is sodium sulfide solution with a Na2S mass fraction of 10%; the acid used for acid-adjusting oxidation is sulfuric acid with a mass fraction of 20%; and the oxidizing agent is hydrogen peroxide with a mass fraction of 20%. Finally, the acid-adjusted and oxidized slurry is fed into a filter press for three rounds of filtration to obtain purified electrolyte and oxidized purified residue. The resulting purified electrolyte is then used in subsequent electrolysis operations; it is fed into an electrolytic cell for electrolysis at a temperature of 38℃ and a cathode current density of 320 A / m. 2 The cathode manganese deposition cycle is 22 hours, and cathode electrolytic manganese is obtained; h) The obtained cathode electrolytic manganese was sequentially passivated, stripped and packaged to finally obtain the electrolytic manganese product with a purity of 99.78%.

[0067] Example 3 In this embodiment, the grade of Mn in the manganese carbonate ore is 28.96%, the grade of SiO2 is 17.84%, the grade of Al2O3 is 4.35%, the grade of MgO is 8.74%, and the grade of CaO is 9.52%.

[0068] The method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification in this embodiment includes the following steps: a) Manganese carbonate ore is fed into a crushing and screening system via a conveyor belt for crushing and screening to obtain ore with a first particle size of less than 10 mm. b) The first-size mineral particles (less than 10 mm) obtained in step a) are fed into a dry roller-type high-intensity magnetic separator for roughing. The roughing magnetic induction intensity is 1.0 T, the roughing frequency converter frequency is 40 Hz, and the angle between the baffle and the roller is 60°, yielding roughing concentrate and roughing tailings. The roughing concentrate yield is 82.40%, the Mn grade is 33.40%, and the Mn recovery rate is 95.03%. The roughing tailings are further fed into a dry roller-type high-intensity magnetic separator for scavenging. The scavenging magnetic induction intensity is 1.0 T, the scavenging frequency converter frequency is 35 Hz, and the angle between the baffle and the roller is 60°, yielding scavenging concentrate and final pre-selected tailings. The scavenging concentrate yield is 6.20%, the Mn grade is 13.90%, and the Mn recovery rate is 2.98%. The final pre-selected tailings yield is 11.40%, the Mn grade is 5.06%, and the Mn recovery rate is 1.99%. The roughing concentrate and scavenging concentrate were combined and used as pre-concentration concentrate for subsequent two-stage ball milling operations. The yield of the combined pre-concentration concentrate was 88.60%, the Mn grade was 32.04%, and the total Mn recovery rate was 98.01%. c) The pre-selected concentrate obtained in step b) is fed into a first-stage ball mill and a second-stage ball mill for grinding, so that the manganese carbonate minerals are fully dissociated to obtain a second-size grinding product that meets the requirements of subsequent pulping and chemical leaching; and the content of the -0.074mm particle size in the grinding product after the second-stage ball mill is controlled to be more than 84%. d) The grinding product obtained in step c) is fed into a pulping tank and water is added for pulping to obtain a homogeneous slurry with a slurry concentration of 36%. e) The slurry obtained in step d) is fed into a chemical reaction tank to react with sulfuric acid. The reaction liquid-solid ratio is 5.5:1, the sulfuric acid concentration is 1.00 mol / L, the chemical reaction temperature is 72℃, and the chemical reaction time is 95 min. This converts the manganese minerals in the manganese carbonate ore into manganese sulfate and enters the liquid phase to obtain the leaching slurry. f) The leachate obtained in step e) is subjected to multi-stage purification treatment, which includes neutralization and iron removal, primary pressure filtration, sulfidation, secondary pressure filtration, acid adjustment and oxidation, and tertiary pressure filtration. Specifically: First, a neutralizing agent is added to the leachate for neutralization and iron removal, the pH of the system is adjusted to 4.9, and the mixture is stirred at 62°C for 30 minutes to precipitate iron impurities in the leachate; then, the resulting slurry is sent to a pressure filter for primary filtration to obtain primary filtrate and iron-removed slag; then, a sulfiding agent is added to the primary filtrate for sulfidation at 40°C for 25 minutes to precipitate heavy metal impurities such as copper, lead, zinc, cadmium, nickel, and cobalt in the solution. The sulfided slurry is then fed into a filter press for secondary filtration to obtain secondary filtrate and sulfided slag. The secondary filtrate is then fed into an acid-adjusting oxidation tank, where sulfuric acid is added to adjust the acidity, and an oxidizing agent is added for oxidation. The acid-adjusting oxidation temperature is 45℃, and the reaction time is 30 minutes to further remove residual impurities. The neutralizing agent is ammonia water with a mass fraction of 15%; the sulfiding agent is sodium sulfide solution with a Na2S mass fraction of 10%; the acid used for acid-adjusting oxidation is sulfuric acid with a mass fraction of 20%; and the oxidizing agent is hydrogen peroxide with a mass fraction of 20%. Finally, the acid-adjusted and oxidized slurry is fed into a filter press for three rounds of filtration to obtain purified electrolyte and oxidized purified residue. The resulting purified electrolyte is then used in subsequent electrolysis operations; it is fed into an electrolytic cell for electrolysis at a temperature of 40℃ and a cathode current density of 350 A / m. 2 The cathode manganese deposition cycle is 24 hours, and cathode electrolytic manganese is obtained; h) The obtained cathode electrolytic manganese was sequentially passivated, stripped and packaged to finally obtain the electrolytic manganese product with a purity of 99.84%.

[0069] Example 4 In this embodiment, the grade of Mn in the manganese carbonate ore is 24.72%, the grade of SiO2 is 20.88%, the grade of Al2O3 is 6.42%, the grade of MgO is 11.76%, and the grade of CaO is 13.54%.

[0070] The method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification in this embodiment includes the following steps: a) Manganese carbonate ore is fed into a crushing and screening system via a conveyor belt for crushing and screening to obtain ore with a first particle size of less than 10 mm. b) The first-size mineral particles (less than 10 mm) obtained in step a) are fed into a dry roller-type high-intensity magnetic separator for roughing. The roughing magnetic induction intensity is 1.0 T, the roughing frequency converter frequency is 30 Hz, and the angle between the baffle and the roller is 50°, yielding roughing concentrate and roughing tailings. The roughing concentrate yield is 73.60%, the Mn grade is 30.45%, and the Mn recovery rate is 90.66%. The roughing tailings are further fed into a dry roller-type high-intensity magnetic separator for scavenging. The scavenging magnetic induction intensity is 1.0 T, the scavenging frequency converter frequency is 30 Hz, and the angle between the baffle and the roller is 50°, yielding scavenging concentrate and final pre-selected tailings. The scavenging concentrate yield is 8.80%, the Mn grade is 11.80%, and the Mn recovery rate is 4.20%. The final pre-selected tailings yield is 17.60%, the Mn grade is 7.22%, and the Mn recovery rate is 5.14%. The roughing concentrate and scavenging concentrate were combined and used as pre-concentration concentrate for subsequent two-stage ball milling operations. The yield of the combined pre-concentration concentrate was 82.40%, the Mn grade was 28.46%, and the total Mn recovery rate was 94.86%. c) The pre-selected concentrate obtained in step b) is fed into a first-stage ball mill and a second-stage ball mill for grinding, so that the manganese carbonate minerals are fully dissociated to obtain a second-size grinding product that meets the requirements of subsequent pulping and chemical leaching; and the content of the -0.074mm particle size in the grinding product after the second-stage ball mill is controlled to be more than 80%. d) The grinding product obtained in step c) is fed into a pulping tank and water is added for pulping to obtain a homogeneous slurry with a slurry concentration of 33%. e) The slurry obtained in step d) is fed into a chemical reaction tank to react with sulfuric acid. The reaction liquid-solid ratio is 6:1, the sulfuric acid concentration is 1.10 mol / L, the chemical reaction temperature is 78℃, and the chemical reaction time is 110 min. This converts the manganese minerals in the manganese carbonate ore into manganese sulfate and enters the liquid phase to obtain the leaching slurry. f) The leachate obtained in step e) is subjected to multi-stage purification treatment, which includes neutralization and iron removal, primary pressure filtration, sulfidation, secondary pressure filtration, acid adjustment and oxidation, and tertiary pressure filtration. Specifically: First, a neutralizing agent is added to the leachate for neutralization and iron removal, the pH of the system is adjusted to 5.0, and the mixture is stirred at 65°C for 35 minutes to precipitate iron impurities in the leachate; then, the resulting slurry is sent to a pressure filter for primary filtration to obtain primary filtrate and iron-removed slag; then, a sulfiding agent is added to the primary filtrate for sulfidation at 42°C for 28 minutes to precipitate heavy metal impurities such as copper, lead, zinc, cadmium, nickel, and cobalt in the solution. The sulfided slurry is then fed into a filter press for secondary filtration to obtain secondary filtrate and sulfided slag. The secondary filtrate is then fed into an acid-adjusting oxidation tank, where sulfuric acid is added to adjust the acidity, and an oxidizing agent is added for oxidation. The acid-adjusting oxidation temperature is 48℃, and the reaction time is 35 minutes to further remove residual impurities. The neutralizing agent is ammonia water with a mass fraction of 15%; the sulfiding agent is sodium sulfide solution with a Na2S mass fraction of 10%; the acid used for acid-adjusting oxidation is sulfuric acid with a mass fraction of 20%; and the oxidizing agent is hydrogen peroxide with a mass fraction of 20%. Finally, the acid-adjusted and oxidized slurry is fed into a filter press for three rounds of filtration to obtain purified electrolyte and oxidized purified residue. The resulting purified electrolyte is then used in subsequent electrolysis operations; it is fed into an electrolytic cell for electrolysis at a temperature of 45℃ and a cathode current density of 380 A / m. 2 The cathode manganese deposition cycle is 26 hours, and cathode electrolytic manganese is obtained; h) The obtained cathode electrolytic manganese was sequentially passivated, stripped and packaged to finally obtain the electrolytic manganese product with a purity of 99.76%.

[0071] Example 5 In this embodiment, the grade of Mn in the manganese carbonate ore is 30.18%, the grade of SiO2 is 15.72%, the grade of Al2O3 is 3.86%, the grade of MgO is 7.24%, and the grade of CaO is 8.36%.

[0072] The method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification in this embodiment includes the following steps: a) Manganese carbonate ore is fed into a crushing and screening system via a conveyor belt for crushing and screening to obtain ore with a first particle size of less than 10 mm. b) The first-size mineral particles (less than 10 mm) obtained in step a) are fed into a dry roller-type high-intensity magnetic separator for roughing. The roughing magnetic induction intensity is 1.0 T, the roughing frequency converter frequency is 38 Hz, and the angle between the baffle and the roller is 58°, yielding roughing concentrate and roughing tailings. The roughing concentrate yield is 84.40%, the Mn grade is 34.00%, and the Mn recovery rate is 95.08%. The roughing tailings are further fed into a dry roller-type high-intensity magnetic separator for scavenging. The scavenging magnetic induction intensity is 1.0 T, the scavenging frequency converter frequency is 35 Hz, and the angle between the baffle and the roller is 58°, yielding scavenging concentrate and final pre-selected tailings. The scavenging concentrate yield is 5.60%, the Mn grade is 15.00%, and the Mn recovery rate is 2.78%. The final pre-selected tailings yield is 10.00%, the Mn grade is 6.44%, and the Mn recovery rate is 2.13%. The roughing concentrate and scavenging concentrate were combined and used as pre-concentration concentrate for subsequent two-stage ball milling operations. The yield of the combined pre-concentration concentrate was 90.00%, the Mn grade was 32.82%, and the total Mn recovery rate was 97.86%. c) The pre-selected concentrate obtained in step b) is fed into a first-stage ball mill and a second-stage ball mill for grinding, so that the manganese carbonate minerals are fully dissociated to obtain a second-size grinding product that meets the requirements of subsequent pulping and chemical leaching; and the content of the -0.074mm particle size in the grinding product after the second-stage ball mill is controlled to be more than 85%; d) The grinding product obtained in step c) is fed into a pulping tank and water is added for pulping to obtain a homogeneous slurry with a slurry concentration of 37%. e) The slurry obtained in step d) is fed into a chemical reaction tank to react with sulfuric acid. The reaction liquid-solid ratio is 7:1, the sulfuric acid concentration is 1.20 mol / L, the chemical reaction temperature is 82℃, and the chemical reaction time is 120 min. This converts the manganese minerals in the manganese carbonate ore into manganese sulfate and enters the liquid phase to obtain the leaching slurry. f) The leachate obtained in step e) undergoes a multi-stage purification process, which sequentially includes neutralization and iron removal, primary pressure filtration, sulfidation, secondary pressure filtration, acid adjustment and oxidation, and tertiary pressure filtration. Specifically: First, a neutralizing agent is added to the leachate for neutralization and iron removal, adjusting the pH of the system to 4.7. The mixture is stirred at 60°C for 28 minutes to precipitate iron impurities in the leachate. Then, the resulting slurry is fed into a pressure filter for primary filtration to obtain primary filtrate and iron-removed slag. Next, a sulfiding agent is added to the primary filtrate for sulfidation at 39°C for 22 minutes to precipitate heavy metal impurities such as copper, lead, zinc, cadmium, nickel, and cobalt. Finally, the sulfidated slurry is fed into a pressure filter. A second filtration process was performed to obtain a secondary filtrate and sulfide residue. The secondary filtrate was then fed into an acid-adjusting oxidation tank, where sulfuric acid was added to adjust the acidity, and an oxidizing agent was added to initiate the oxidation reaction. The acid-adjusting oxidation temperature was 43℃, and the reaction time was 27 minutes to further remove residual impurities. The neutralizing agent was ammonia water with a mass fraction of 15%. The sulfiding agent was a mixed sodium sulfide solution with a mass fraction of 10% Na2S, 5% L-hydroxyproline, and 2% α-lipoic acid. The acid used for acid-adjusting oxidation was sulfuric acid with a mass fraction of 20%, and the oxidizing agent was hydrogen peroxide with a mass fraction of 20%. Finally, the acid-adjusted and oxidized slurry is fed into a filter press for three rounds of filtration to obtain purified electrolyte and oxidized purified residue. The resulting purified electrolyte is then used in subsequent electrolysis operations; it is fed into an electrolytic cell for electrolysis at a temperature of 42℃ and a cathode current density of 360 A / m. 2 The cathode manganese deposition cycle is 25 hours, and cathode electrolytic manganese is obtained; h) The obtained cathode electrolytic manganese was sequentially passivated, stripped and packaged to finally obtain the electrolytic manganese product with a purity of 99.92%.

[0073] Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification, characterized in that: Includes the following steps: a) The manganese carbonate ore is crushed and screened to obtain the first particle size ore. b) The ore of the first particle size is subjected to dry high-intensity magnetic separation pre-selection and tailings removal to obtain pre-selected concentrate; c) Grind the pre-selected concentrate to obtain a ground product of the second particle size; d) The grinding product is mixed with water or return liquid and subjected to pulping treatment to obtain a slurry; e) The slurry is mixed with sulfuric acid and chemically leached to obtain a leaching slurry; f) The leachate slurry is subjected to multi-stage purification treatment, which includes at least sequential neutralization and iron removal, sulfidation and impurity removal, and acid adjustment and oxidation processes, and solid-liquid separation is performed after each process to obtain purified electrolyte. g) Electrolyze the purified electrolyte to obtain cathode electrolytic manganese.

2. The method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification according to claim 1, characterized in that: The first particle size is less than 10 mm, preferably more than 90% of which are less than 8 mm; And / or, the manganese carbonate ore has a Mn grade of 20%-32%, a SiO2 grade of 14%-22%, an Al2O3 grade of 3%-8%, an MgO grade of 6%-14%, and a CaO grade of 6%-16%.

3. The method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification according to claim 1, characterized in that: The dry high-intensity magnetic separation pre-selection tailings disposal specifically includes: feeding the first-size ore into a dry roller high-intensity magnetic separator for a roughing and scavenging operation, wherein the roughing operation obtains roughing concentrate and roughing tailings, and the scavenging operation processes the roughing tailings to obtain scavenging concentrate and final tailings; the roughing concentrate and the scavenging concentrate are combined as the pre-selection concentrate.

4. The method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification according to claim 1, characterized in that: The magnetic induction intensity of the coarse selection operation and / or the sweeping operation is independently 0.8T-1.2T, preferably 1.0T; And / or, the frequency of the inverter for the coarse selection operation is 30Hz-40Hz, and the frequency of the inverter for the sweep selection operation is 30Hz-40Hz. And / or, the tailings baffle of the dry roller strong magnetic separator has an angle of 50°-60° with the roller surface.

5. The method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification according to claim 1, characterized in that: The grinding process is a two-stage ball milling process, including a first-stage ball milling and a second-stage ball milling, and the content of particles with the second particle size of -0.074mm accounts for more than 80%; And / or, the mass concentration of the slurry prepared in step d) is 30%-45%.

6. The method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification according to claim 1, characterized in that: The conditions for chemical leaching in step e) are as follows: liquid-to-solid mass ratio of (4-8):1, sulfuric acid concentration of 0.6 mol / L-1.4 mol / L, leaching temperature of 40℃-90℃, and leaching time of 30 min-150 min.

7. The method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification according to claim 1, characterized in that: The multi-stage purification process in step f) specifically includes: f1) Add a neutralizing agent to the leaching slurry for neutralization and iron removal treatment, and perform a first pressure filtration on the resulting slurry to obtain primary filtrate and iron removal slag; f2) Add a sulfiding agent to the primary filtrate for sulfidation and impurity removal treatment, and then perform a second pressure filtration on the resulting slurry to obtain secondary filtrate and sulfidation residue; f3) Add acid and oxidant to the secondary filtrate for acid adjustment and oxidation treatment, and then perform a third pressure filtration on the resulting slurry to obtain the purified electrolyte and the oxidized purification residue.

8. The method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification according to claim 7, characterized in that: In step f1), the conditions for neutralization and iron removal treatment are: pH value controlled at 4.5-5.5, temperature at 50℃-70℃, and time at 20min-40min. And / or, in step f2), the conditions for the sulfurization impurity removal treatment are: temperature of 35℃-45℃ and time of 15min-30min; And / or, in step f3), the conditions for the acid-adjusting oxidation treatment are: temperature of 40℃-50℃ and time of 20min-40min.

9. The method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification according to claim 1, characterized in that: The electrolysis conditions in step g) are: electrolysis temperature of 30℃-50℃, and cathode current density of 300A / m. 2 -400 A / m 2 The electrolysis cycle is 20-30 hours.

10. The method for preparing electrolytic manganese from manganese carbonate ore through dry polishing pre-selection and multi-stage purification according to claim 1, characterized in that: It also includes step h): sequentially passivating, stripping and packaging the cathode electrolytic manganese to obtain the electrolytic manganese product; preferably, the manganese purity of the electrolytic manganese product is not less than 99.75%.

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