Production line and production method of electrolytic manganese metal

Abstract

The production line comprises a crushing and grinding device, a liquid preparation system, an electrolysis system, a post-treatment system and a manganese residue treatment system, and the liquid preparation system comprises a slurrying barrel, a chemical combination barrel, a first filter press, a vulcanization pool, a second filter press, a purification tank, a third filter press and an elevated tank. The crushing and grinding device is communicated with the slurrying barrel, an outlet of the slurrying barrel is communicated with the chemical combination barrel, the chemical combination barrel is communicated with the first filter press, the first filter press is communicated with the vulcanization pool, the vulcanization pool is communicated with the second filter press, the second filter press is communicated with the purification tank, the purification tank is communicated with the third filter press, the third filter press is communicated with the head tank, and the head tank is communicated with the electrolysis system. The anolyte storage tank is respectively communicated with the slurrying barrel and the chemical combination barrel, and the first filter press, the second filter press and the third filter press are connected with a manganese slag treatment system. According to the production line, the leaching rate and the impurity removal rate can be increased, manganese slag recycling is achieved, and generation and emission of pollutants in the production process are reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of electrolytic manganese production, and in particular to a production line and a production method of electrolytic manganese. Background Art

[0002] Metallic manganese is widely used in various fields such as steel smelting, nonferrous metallurgy, electronic technology, chemical industry, environmental protection, food hygiene, welding rod industry, aerospace industry, etc. China is currently the world's largest producer and consumer of electrolytic metallic manganese. Currently, the production of electrolytic metallic manganese mainly adopts the hydrometallurgical process of acid leaching electrolysis.

[0003] In the process of using the existing acid leaching electrolytic hydrometallurgical process, a large amount of waste gas, waste water and waste residue are generated. These wastes will not only cause environmental pollution, but also cause waste of resources, which does not meet the requirements of energy conservation and emission reduction and circular production. A production method of electrolytic manganese disclosed in CN112553481A includes the steps of leaching, impurity removal, extraction, stripping, electrolysis and recovery of ammonia nitrogen and magnesium. The patent divides the liquid circulation into two parts, greatly reduces the accumulation of impurities in the circulating solution, effectively increases the number of cycles, and the treated ammonia nitrogen and magnesium can be directly recycled, but the leaching rate and impurity removal rate of manganese ore are low, and more manganese slag will still be produced. The manganese slag is also not effectively comprehensively utilized to realize resource utilization. Therefore, there is an urgent need for a production process that is environmentally friendly, has good economic benefits and high resource utilization. Summary of the invention

[0004] The main purpose of the present invention is to overcome the defects of the above-mentioned background technology and provide a production line and a production method for electrolytic manganese.

[0005] To achieve the above-mentioned purpose, the production line of electrolytic manganese metal proposed in the present invention includes a crushing and grinding device, a liquid preparation system, an electrolysis system, a post-treatment system and a manganese slag treatment system, wherein the liquid preparation system includes a pulping barrel, a combination barrel, a first filter press, a sulfidation tank, a second filter press, a purification tank, a third filter press and a high-level tank, wherein the crushing and grinding device is connected to the pulping barrel, the pulping barrel outlet is connected to the combination barrel, the combination barrel is connected to the first filter press, the filtrate outlet of the first filter press is connected to the sulfidation tank, the sulfidation tank is connected to the second filter press, and the filtrate outlet of the second filter press is connected to the sulfidation tank. The filtrate outlet of the third filter press is connected to the high-level tank, and the high-level tank is connected to the electrolysis system. The plate after electrolysis by the electrolysis system is sent to the post-treatment system for treatment. The anolyte produced after electrolysis by the electrolysis system is sent to the anolyte storage tank through the return pipe. The outlet of the anolyte storage tank is connected to the pulping barrel, and the slag outlet of the anolyte storage tank is connected to the chemical barrel. The filtrate outlets of the first filter press, the second filter press and the third filter press are connected to the manganese slag treatment system. After the manganese carbonate ore enters the crushing and grinding device for grinding, it is slurried with the anolyte produced after electrolysis in the pulping barrel, and then enters the chemical barrel for chemical reaction. After the chemical reaction, the leaching liquid is subjected to three purification processes of coarse filtration, sulfidation and fine filtration in sequence, which effectively improves the leaching and purification efficiency.

[0006] Furthermore, the combination barrel is connected to a sulfuric acid barrel, an oxidant barrel, an ammonia barrel and an acid mist outlet pipe, the acid mist outlet pipe is connected in series with an acid mist absorption tower, an induced draft fan and a first smoke exhaust pipe, the sulfidation tank is connected to a sulfidation agent barrel, the purification tank is connected to an aluminum sulfate barrel and an activated carbon barrel, and the high-level tank is connected to a selenium dioxide barrel. The acid mist generated during the leaching process is absorbed and treated by the acid mist absorption tower to prevent the acid mist from polluting the environment.

[0007] Furthermore, the post-processing system includes a post-processing integrated machine, an anode plate washing machine, a bubble plate tank, a cathode plate washing machine, a sewage treatment station and a circulating water tank, the bubble plate tank is connected to the return liquid pipe, the anode plate washing machine and the cathode plate washing machine are connected to the sewage treatment station, and the circulating water tank is connected to the sewage treatment station. The cathode plate after electrolysis by the electrolysis system is sent to the post-processing integrated machine for treatment to obtain an electrolytic manganese product, and the anode plate is sent to the anode plate washing machine for washing and reuse. The cathode plate treated by the post-processing integrated machine is sent to the bubble plate tank for soaking treatment and then sent to the cathode plate washing machine for washing and reuse. The wastewater generated in the production process is treated by the sewage treatment station to facilitate the recycling of water resources.

[0008] Furthermore, the manganese slag processing system includes a manganese slag batching tank, a roasting kiln device, a cooling device, a grinding device and a magnetic separation device. The manganese slag batching tank is connected to the inlet of the roasting kiln device, the inlet of the cooling device is connected to the outlet of the roasting kiln device, the outlet of the cooling device is connected to the inlet of the grinding device, and the inlet of the magnetic separation device is connected to the outlet of the grinding device. The manganese slag is thermally activated by the roasting kiln device to efficiently solidify and stabilize the heavy metal manganese in the manganese slag, and then the magnetic separation device is used to perform magnetic separation to recover the magnetic material, thereby realizing the resource utilization of manganese slag.

[0009] Furthermore, the magnetic separation device includes a weak magnetic iron separation section and a strong magnetic manganese separation section. The manganese slag powder passing through the weak magnetic iron separation section is used to select iron products, and the manganese slag powder passing through the strong magnetic manganese separation section is used to select manganese products. The iron products in the manganese slag are selected through weak magnetic iron separation, and the manganese products in the manganese slag powder are selected through strong magnetic manganese separation. The remaining tailing powder can be sold as building material raw materials.

[0010] Furthermore, the roasting kiln device includes a low-temperature deammoniation section and a high-temperature modification section, the flue gas outlet of the low-temperature deammoniation section is connected to the first dust collector, the outlet of the first dust collector is connected to the condenser, the liquid outlet of the condenser is connected to the ammonia water barrel, the flue gas outlet of the high-temperature modification section is connected to the SNCR denitration equipment, the outlet of the SNCR denitration equipment is connected to the second dust collector, the outlet of the second dust collector is connected to the spray washing tower, the flue gas outlet of the spray washing tower is connected to the second exhaust pipe, and the washing liquid outlet of the spray washing tower is connected to the sedimentation tank. The manganese slag in the low-temperature deammoniation section is preheated and deammonified by utilizing the waste heat generated by the roasting of the high-temperature modification section, and the high-humidity flue gas generated by the preheating is condensed by the condenser to form ammonia water for recycling.

[0011] Furthermore, the combining barrel is provided with a stirring device, which includes a stirring motor, a reducer and a stirring shaft, the output end of the stirring motor is connected to the input end of the reducer, the output end of the reducer is connected to one end of the stirring shaft, the stirring shaft extends from the top center of the combining barrel to the interior of the combining barrel, the stirring shaft is provided with stirring blades, a center wheel is fixedly provided on the upper part of the stirring shaft, the center wheel is meshedly connected with a planetary wheel, the planetary carrier on the planetary wheel is fixed to the inner top wall of the combining barrel, the outer periphery of the planetary wheel is meshedly connected with a gear ring, a stirring frame is connected to the gear ring, the stirring frame is in contact with the inner side wall of the combining barrel, the bottom end of the stirring frame is rotatably sleeved on the lower part of the stirring shaft through a support ring, and a plurality of flexible stirring belts are vertically provided in the stirring frame. By providing a planetary gear system on the stirring shaft, the stirring frame and the stirring blades rotate in opposite directions to achieve stirring. When the stirring frame rotates, the slurry adhering to the side wall of the combining barrel is scraped off. The flexible stirring belt continuously vibrates to transmit the stirring energy further, so that the slurry inside the combining barrel forms turbulence, the stirring is more uniform, and the leaching rate is further improved.

[0012] Furthermore, the combination barrel is connected with a circulation pipe, the circulation pipe is provided with a circulation pump and a heat exchanger, one end of the circulation pipe is connected with the bottom end of the combination barrel, the other end of the circulation pipe is connected with the middle part of the combination barrel, the hot medium inlet of the heat exchanger is connected with the hot medium outlet of the cooling device through the heating pipe, the cold medium inlet of the cooling device is connected with the circulation water pool through the cooling water pipe, the cooling water pipe is provided with a cooling water pump, the cold medium outlet of the heat exchanger is connected with the circulation water pool through the return pipe, the heating pipe and the cooling water pipe are connected with a regulating pipe, and the regulating pipe and the cooling water pipe are respectively provided with regulating valves. The slurry in the combination barrel is drawn out by the circulation pump and flows through the heat exchanger and then returns to the combination barrel, and heat is exchanged with the hot water after heat exchange by the cooling device, and the leached slurry is heated to ensure that the temperature during leaching is stable between 50°C and 60°C, and the heat of the high-temperature manganese slag is fully utilized, energy consumption is reduced, and the leaching rate of manganese ore is further improved.

[0013] Furthermore, the upper end of the circulation pipe is connected with a distribution ring, which surrounds the outer wall of the combination barrel and is provided with a plurality of branch pipes connected with the inside of the combination barrel. The distribution ring is used to pass the slurry from the periphery of the combination barrel into the inside of the combination barrel to ensure temperature balance.

[0014] The present invention also provides a method for producing electrolytic manganese metal, comprising the following steps:

[0015] S1, putting the manganese ore into a crushing and grinding device for powdering to obtain ore powder with a particle size of 85-100 mesh;

[0016] S2, measuring the mineral powder and putting it into the pulping barrel, adding the anode liquid stored in the anode liquid storage tank into the pulping barrel and stirring, so that the mineral powder and the anode liquid are mixed into a slurry;

[0017] S3, conveying the slurry prepared in step S2 to a combination barrel, and adding concentrated sulfuric acid stored in a sulfuric acid barrel into the combination barrel to adjust the pH value to between 1 and 3 for leaching reaction, starting a stirring device for stirring during the leaching reaction, and stirring the stirring shaft with a stirring blade stirring at a speed of 200 r / min at the axis center of the combination barrel, and stirring the stirring frame stirring at a speed of 100 r / min at the periphery of the stirring shaft in the reverse direction, and a plurality of flexible stirring belts continuously shaking during the rotation process;

[0018] S4. After leaching for 2-2.5 hours, add the manganese dioxide stored in the oxidant barrel into the combination barrel for oxidation reaction, and add the anode mud at the bottom of the anode liquid storage tank when the residual acid in the combination barrel is 2-3g / L;

[0019] S5. After the entire leaching reaction lasts for 3 hours, add the 15% concentration of ammonia water stored in the ammonia water barrel into the combination barrel for neutralization reaction, so that the pH value in the combination barrel is adjusted to 6.0-6.5;

[0020] S6, pumping the slurry leached in step S5 to the first filter press for filtration to obtain a primary filtrate and a primary filter residue; transporting the primary filtrate to a sulfidation tank and adding the SDD agent stored in the sulfidation agent barrel for sulfidation and impurity removal, and after the heavy metal qualitative analysis in the primary filtrate is qualified, using the second filter press for solid-liquid separation to obtain a secondary filtrate and a secondary filter residue; the secondary filtrate enters a purification tank, and aluminum sulfate stored in an aluminum sulfate barrel is added to the purification tank to make the harmful impurities in the secondary filtrate condense and coarsen the particles and settle, and then adding activated carbon stored in an activated carbon barrel for adsorption and standing for 24 hours, and the solution after adsorption and standing is sent to a third filter press for fixed liquid separation to obtain a tertiary filtrate and a tertiary filter residue, and the tertiary filtrate is sent to a high-level tank for electrolysis;

[0021] S7, the primary filter residue, secondary filter residue and tertiary filter residue in step S6 are sent to the manganese slag batching tank, and the sulfur-fixing agent and heavy metal solidifying agent are added and stirred, and then sent to the low-temperature deammoniation section of the roasting kiln device for drying and deammoniation. The generated ammonia-containing high-humidity flue gas is precipitated and dusted in the first dust collector and then enters the condenser to condense into ammonia water, and the ammonia water is transported back to the ammonia water bucket; the manganese slag after deammoniation enters the high-temperature modification section for roasting, the roasting temperature is 950°C, the residence time is 1 hour, the flue gas generated by the roasting enters the SNCR denitrification equipment, the second dust removal equipment and the spray washing tower in turn for treatment, the treated tail gas enters the second exhaust pipe for discharge, and the circulating liquid of the spray washing tower regularly enters the sedimentation tank for precipitation treatment to obtain a desulfurized gypsum product;

[0022] S8, sending the roasted manganese slag to a cooling device for cooling. The cooling device is a cooling cylinder with an interlayer. The cooling water stored in a circulating water pool after being treated in a sewage treatment station is introduced into the interlayer of the cooling cylinder. The cooling water is heated and then enters a heat exchanger to exchange heat with the leaching solution circulating from the combination barrel, ensuring that the leaching temperature in the combination barrel is stabilized between 50°C and 60°C.

[0023] S9. The cooled manganese slag is sent to the grinding device for grinding. The ground manganese slag powder is sent to the magnetic separation device to first select the iron product through the weak magnetic iron separation section, and then enter the strong magnetic manganese separation section to select the manganese product. The remaining tailings are taken away as building material raw materials.

[0024] S10. Add the selenium dioxide stored in the selenium dioxide barrel to the high-level tank in step S6, and then send the electrolyte in the high-level tank to the electrolysis system for electrolysis. After the electrolysis, electrolytic manganese is precipitated on the cathode plate and sent to the post-processing integrated machine for passivation, cleaning, drying and peeling to obtain an electrolytic manganese product. The cathode plate after peeling is sent to the bubble plate tank and is soaked in the anode liquid in the anode liquid storage tank. The soaked cathode plate is sent to the cathode plate washing machine for washing, and the anode plate is sent to the anode plate washing machine for washing. The wastewater generated by washing is sent to the sewage treatment station for treatment.

[0025] The beneficial effects of the present invention include: grinding the manganese ore into powder, mixing and stirring the powder with the anode liquid to form a slurry, and then adding concentrated sulfuric acid to carry out a leaching reaction, thereby increasing the contact between manganese carbonate and sulfuric acid, improving the leaching rate, and reducing the amount of waste residue formed; the acid mist waste gas formed by the leaching reaction is treated by an acid mist absorption tower to avoid polluting the environment; the leaching liquid is added to the anode mud in the later stage of the oxidation reaction to further oxidize the divalent iron ions in the solution into trivalent iron ions, and the manganese in the anode mud can also be recovered to increase the manganese recovery rate; then the leaching liquid is subjected to three-stage filtration by coarse filtration, sulfidation, and fine filtration to separate the solid from the liquid, effectively improving the purification effect; the manganese slag generated by the three-stage filtration is sent to the manganese slag treatment system for recovery and treatment, and the entire production can effectively improve the leaching rate and the impurity removal rate, improve the resource utilization efficiency, realize the resource utilization of manganese slag, reduce the generation and discharge of pollutants in the production process, and reduce the harm to human health and the environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a process flow chart of the production line of electrolytic manganese in an embodiment of the present invention.

[0027] Figure 2 Schematic diagram of the connection of the combination barrel in the embodiment of the present invention.

[0028] Figure 3 Schematic diagram of a stirring device in an embodiment of the present invention.

[0029] Figure 4 It is a flow chart of the production method of the present invention.

[0030] Figure numerals: 1 crushing and grinding device; 2 pulping barrel; 3 combination barrel; 301 sulfuric acid barrel; 302 oxidant barrel; 303 ammonia barrel; 304 acid mist outlet pipe; 305 acid mist absorption tower; 306 induced draft fan; 307 first smoke exhaust pipe; 308 stirring device; 3081 stirring motor; 3082 reducer; 3083 stirring shaft; 3084 stirring blade; 3085 center wheel; 3086 planetary gear; 3087 planetary carrier; 3088 gear ring; 3089 stirring frame; 30810 support ring; 30811 flexible stirring belt; 309 circulation pipe; 3091 circulation pump; 3092 heat exchanger; 3093 heating pipe; 3094 cooling water pipe; 3095 cooling water pump; 3096 return pipe; 3097 regulating pipe; 3098 regulating valve; 3099 distribution ring ;3010;4 the first filter press;5 sulfidation tank;501 sulfidation agent barrel;6 the second filter press;7 purification tank;701 aluminum sulfate barrel;8 the third filter press;9 high-level tank;901 selenium dioxide barrel;10 electrolysis system;11 anode liquid storage tank;1101 post-processing integrated machine;1102 anode plate washing machine;1103 bubble plate tank;1104 cathode plate washing machine;1105 sewage treatment station;1106 circulating water tank;1201 manganese slag batching tank;1202 roasting kiln device;1203 cooling device;1204 grinding device;1205 magnetic separation device;1206 the first dust collector;1207 condenser;1208SNCR denitrification equipment;1209 the second dust collector;1210 spray washing tower;1211 the second chimney;1212 sedimentation tank. DETAILED DESCRIPTION

[0031] In order to make the technical problems, technical solutions and beneficial effects to be solved by the embodiments of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0032] It should be noted that when a component is referred to as being "fixed to" or "disposed on" another component, it can be directly on the other component or indirectly on the other component. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or indirectly connected to the other element. In addition, connection can be used for both fixing and circuit connection.

[0033] It should be understood that the terms "length", "width", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", etc., indicating the orientation or position relationship, are based on the orientation or position relationship shown in the accompanying drawings, and are only for the convenience of describing the embodiments of the present invention 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 cannot be understood as a limitation on the present invention.

[0034] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the features. In the description of the embodiments of the present invention, the meaning of "plurality" is two or more, unless otherwise clearly and specifically defined.

[0035] Example 1

[0036] See also Figures 1 to 3The production line of electrolytic manganese metal disclosed in the present invention comprises a crushing and grinding device 1, a liquid preparation system, an electrolysis system 10, a post-treatment system and a manganese slag treatment system which are interconnected. The liquid preparation system comprises a pulping barrel 2, a chemical combination barrel 3, a first filter press 4, a sulfidation tank 5, a second filter press 6, a purification tank 7, a third filter press 8 and a high-level tank 9. The crushing and grinding device 1 is connected to the pulping barrel 2. Specifically, the crushing and grinding device 1 comprises a primary crusher (not shown), a secondary crusher (not shown) and a vertical mill (not shown) purchased from outside. After two-stage crushing, the manganese ore is sent to the vertical mill for grinding. The crusher and the vertical mill are both closed. The dust generated by crushing and grinding is removed by a bag dust collector (not shown). The outlet of the pulping barrel 2 is connected to the chemical combination barrel 3. The outlet of the chemical combination barrel 3 is connected with the first filter press 4, the filtrate outlet of the first filter press 4 is connected with the sulfidation tank 5, the outlet of the sulfidation tank 5 is connected with the second filter press 6, the filtrate outlet of the second filter press 6 is connected with the purification tank 7, the outlet of the purification tank 7 is connected with the third filter press 8, the filtrate outlet of the third filter press 8 is connected with the high-level tank 9, the high-level tank 9 is connected with the electrolysis system 10, the electrode plate after electrolysis by the electrolysis system 10 is sent to the post-processing system for treatment, the anolyte generated after electrolysis by the electrolysis system 10 is sent back to the anolyte storage tank 11 through the return pipe for reuse, the liquid outlet of the anolyte storage tank 11 is connected with the pulping barrel 2, the slag outlet of the anolyte storage tank 11 is connected with the chemical combination barrel 3, the first filter press 4, the second filter press 6 and the third filter press The filter residue outlet of the filter 8 is connected to the manganese residue treatment system. The combination barrel 3 is connected to a sulfuric acid barrel 301, an oxidant barrel 302, an ammonia barrel 303 and an acid mist outlet pipe 304. The acid mist outlet pipe 304 is connected in series with an acid mist absorption tower 305, an induced draft fan 306 and a first exhaust chimney 307 in sequence. The acid mist and other waste gases generated during the leaching reaction are treated in the acid mist absorption tower 305 and then discharged to avoid acid mist polluting the environment; the sulfidation tank 5 is connected to a sulfidation agent barrel 501, the purification tank 7 is connected to an aluminum sulfate barrel 701 and an activated carbon barrel 702, and the high-level tank 9 is connected to a selenium dioxide barrel 901; the post-processing system includes a post-processing integrated machine 1101, an anode plate washing machine 1102, a bubble plate tank 1103, and a cathode plate washing machine 1104, sewage treatment station 1105 and circulating water pool 1106, the bubble plate tank 1103 is connected with the return pipe entering the anode liquid storage tank 11, the anode liquid is introduced into the bubble plate tank 1103 for soaking the cathode plate, the anode plate rinser 1102 and the cathode plate rinser 1104 are connected with the sewage treatment station 1105, the circulating water pool 1106 is connected with the sewage treatment station 1105, the cathode plate after electrolysis by the electrolysis system 10 is sent to the post-processing integrated machine 1101 for treatment to obtain the electrolytic manganese product, the anode plate is sent to the anode plate rinser 1102 for rinsing treatment and reuse, the cathode plate after treatment by the post-processing integrated machine 1101 is sent to the bubble plate tank 1103 for soaking treatment and then sent to the cathode plate rinser 1104 for rinsing treatment and reuse.

[0037] In this embodiment, the manganese ore is ground into powder and then enters the pulping barrel 2 to mix and stir with the anode liquid and then enters the combining barrel 3. After the anode liquid and the manganese ore powder are fully mixed and slurried, concentrated sulfuric acid is added to carry out a leaching reaction, thereby increasing the contact between manganese carbonate and sulfuric acid, improving the leaching rate, and reducing the amount of waste residue formed. The leaching reaction formula is MnCO3+H2SO4=MnSO4+H2O+CO2. The acid mist waste gas formed by the leaching reaction is drawn to the acid mist absorption tower 305 through the induced draft fan 306 for absorption treatment, and the treated tail gas is discharged through the first exhaust chimney 307. To avoid environmental pollution, iron and some heavy metal elements enter the solution after leaching. At this time, high-purity manganese dioxide is added for oxidation reaction to remove iron. When the oxidation reaction is close to the end point, anode mud is added. Since the main component of anode mud is manganese dioxide, the divalent iron ions in the solution are further oxidized into trivalent iron ions. At the same time, the manganese in the anode mud can also be recovered to increase the manganese recovery rate. When the leaching reaches the end point, 15% ammonia water is added for neutralization, and the pH value of the solution is adjusted to 6.0-6.5. At this time, the trivalent iron has been completely hydrolyzed and precipitated, and then leaching is carried out. The liquid is subjected to three-stage filtration for solid-liquid separation, which includes coarse filtration, sulfidation and fine filtration, and effectively improves the purification effect. The filtrate after the first filtration is fed into the sulfidation tank 5 and added with the impurity remover SDD to convert the trace amount of heavy metal impurities such as Cu, Pb and Zn in the leaching liquid into organic polymer compound precipitation, and then the second filtration is carried out to remove the heavy metal impurities. The filtrate of the second filtration is fed into the purification tank 7, and Al2(SO4)3 is first added to condense and coarsen the impurities such as heavy metal sulfides for sedimentation, and then activated carbon is added as a filter aid for filtration. After adsorbing some impurity hydrolyzates, such as saturated MgSO4 crystals and CaSO4 crystals, three press filtration solid-liquid separations are performed to obtain qualified filtrate stored in the high-level tank 9. Before the qualified filtrate enters the electrolysis system 10, 0.1-0.6g / L of selenium dioxide is added to prevent divalent manganese from hydrolyzing to improve the current efficiency. The manganese slag produced by the three-stage press filtration is sent to the manganese slag treatment system for recycling. The production line can effectively improve the leaching rate and impurity removal rate, thereby improving the production efficiency, and the manganese slag can also be effectively and comprehensively recycled to realize resource utilization.

[0038] Example 2

[0039] Please continue reading Figures 1 to 3This embodiment is a specific implementation of the manganese slag processing system in Example 1. The manganese slag processing system in this embodiment includes a manganese slag batching tank 1201, a roasting kiln device 1202, a cooling device 1203, a grinding device 1204 and a magnetic separation device 1205. The manganese slag batching tank 1201 is connected to the inlet of the roasting kiln device 1202, the inlet of the cooling device 1203 is connected to the outlet of the roasting kiln device 1202, the outlet of the cooling device 1203 is connected to the inlet of the grinding device 1204, the inlet of the magnetic separation device 1205 is connected to the outlet of the grinding device 1204, and the magnetic separation device 1205 includes a weak magnetic iron separation section and a strong magnetic manganese separation section. The manganese slag powder passing through the weak magnetic iron separation section is selected into iron products, and the manganese slag powder passing through the strong magnetic manganese separation section is selected into manganese products. The manganese slag from the third-stage filter press is sent to the manganese slag batching tank 1201, where a sulfur-fixing agent (lime) and a heavy metal solidifying agent (heavy metal chelating agent) are added, stirred, and then sent to the roasting kiln device 1202 for roasting, so that the manganese slag undergoes multiple complex chemical reactions such as calcium sulfate crystal transformation and iron-manganese oxide combination in the kiln, thereby achieving thermal activation of the manganese slag and efficient solidification and stabilization of the heavy metal manganese in the slag. The active manganese slag obtained by roasting enters the grinding device 1204 for grinding to obtain manganese slag powder. The manganese slag powder first passes through the weak magnetic iron separation section of the magnetic separation device 1205. (1000-2000Gs) to select iron products, which are collected and sold for processing. After the weak magnetic iron separation stage, the remaining manganese slag powder is selected and then passed through the strong magnetic manganese separation stage (12000-16000Gs) to select manganese products. The selected manganese products are mixed with manganese ore powder and re-put into the pulping barrel 2 for slurry adjustment to leaching and recover manganese metal. The tailings after magnetic separation are sold as building material raw materials, avoiding the waste of manganese slag resources, reducing the storage space and environmental pollution of waste, and bringing good economic benefits to the enterprise.

[0040] Example 3

[0041] Please continue reading Figures 1 to 3In order to further improve the utilization rate of resources in manganese slag, recover ammonia in manganese slag, and solidify heavy metals in slag; this embodiment is based on Example 2, and a low-temperature deamination section and a high-temperature modification section are set in the roasting kiln device 1202; the roasting kiln device 1202 includes a low-temperature deamination section and a high-temperature modification section, the flue gas outlet of the low-temperature deamination section is connected to the first dust collector 1206, the outlet of the first dust collector 1206 is connected to the condenser 1207, and the liquid outlet of the condenser 1207 is connected to the ammonia The water bucket 303 is connected, the flue gas outlet is connected to the spray washing tower 1210, the flue gas outlet of the high-temperature modification section is connected to the SNCR denitrification equipment 1208, the outlet of the SNCR denitrification equipment 1208 is connected to the second dust collector 1209, the outlet of the second dust collector 1209 is connected to the spray washing tower 1210, the flue gas outlet of the spray washing tower 1210 is connected to the second chimney 1211, and the washing liquid outlet of the spray washing tower 1210 is connected to the sedimentation tank 1212. The manganese slag enters the roasting kiln device 1202 and firstly exchanges heat with the high-temperature tail gas in the countercurrent flow in the low-temperature deammoniation section. The heat exchange temperature is between 300-400°C, for example, 300°C, 350°C and 400°C. The waste heat of the high-temperature tail gas generated by the high-temperature modification section is used to dry and deammonify the manganese slag material, and at the same time, the high-temperature tail gas is initially cooled. The ammonia-containing high-humidity flue gas is settled and dusted in the first dust collector 1206, and then enters the condenser 1207 for cooling to produce low-concentration ammonia water, which is recovered in the ammonia water barrel 303 for use in the production process, further improving the utilization rate of ammonia resources in the manganese slag. The remaining tail gas enters the spray washing tower 1210 for washing and is discharged through the second smoke exhaust chimney 1211 after meeting the standards to avoid pollution. environment; the manganese slag after deammoniation enters the high-temperature modification section for roasting, the roasting temperature is 900℃-1000℃, for example, 900℃, 950℃, 1000℃, preferably 950℃, the residence time is 1 hour, to achieve thermal activation of the manganese slag so that the heavy metals in the slag can be efficiently solidified and stabilized. At the same time, the high-temperature flue gas generated by the roasting is cooled by the low-temperature deammoniation section and then treated in sequence through the SNCR denitrification equipment 1208, the second dust collector 1209 and the spray washing tower 1210. The exhaust gas that meets the treatment standards is discharged through the second smoke stack 1211 to avoid polluting the environment. The circulating washing water of the spray washing tower 1210 enters the sedimentation tank 1212 for precipitation, and the desulfurized gypsum product is obtained for sale, thereby further improving the economic benefits.

[0042] Example 4

[0043] See also Figure 2 and Figure 3In order to further improve the leaching rate, this embodiment is provided with a stirring device 308 on the basis of embodiments 1 to 3 on the basis of embodiments 1 to 3 on the combination barrel 3, the stirring device 308 comprises a stirring motor 3081, a reducer 3082 and a stirring shaft 3083, the output end of the stirring motor 3081 is connected to the input end of the reducer 3082, the output end of the reducer 3082 is connected to one end of the stirring shaft 3083, the stirring shaft 3083 extends from the top center of the combination barrel 3 to the inside of the combination barrel 3, the stirring shaft 3083 is provided with a stirring blade 3084, and the upper part of the stirring shaft 3083 is fixedly provided with a central The center wheel 3085 is meshed with the planetary wheel 3086. The planetary frame 3087 on the planetary wheel 3086 is fixed on the inner top wall of the chemical barrel 3. The outer periphery of the planetary wheel 3086 is meshed with the gear ring 3088. The gear ring 3088 is connected with the stirring frame 3089. The stirring frame 3089 is in contact with the inner side wall of the chemical barrel 3. The bottom end of the stirring frame 3089 is rotatably sleeved on the lower part of the stirring shaft 3083 through the support ring 30810 to prevent the stirring frame 3089 from axial movement. A plurality of flexible stirring belts 30811 are vertically arranged in the stirring frame 3089. When the leaching reaction is carried out in the chemical barrel 3, the stirring device 308 is used to continuously stir the mixture to improve the leaching rate. Since the volume of the chemical barrel 3 is 400m 3 , the diameter is large, and a conventional agitator is prone to dead zones during stirring, resulting in uneven stirring and affecting the leaching rate. Therefore, a planetary gear system is set, and a center wheel 3085 is set on the stirring shaft 3083 as a driving wheel. The planetary frame 3087 is fixed so that the rotation of the ring gear 3088 is opposite to that of the center wheel 3085. The stirring frame 3089 is fixed on the ring gear 3088 and rotates in the opposite direction to the stirring blade 3084 for stirring. When the stirring frame 3089 rotates, it scrapes off the slurry stuck to the side wall of the combining barrel 3, and the flexible stirring belt 30811 vibrates to transmit the stirring energy farther. The stirring frame 3089 and the flexible stirring belt 30811 simultaneously block the slurry driven by the stirring blade 3084 to form turbulence in the slurry, making the stirring more uniform, thereby further improving the leaching rate.

[0044] Example 5

[0045] In order to stabilize the temperature of the slurry in the combination barrel 3 at 50℃-60℃ during the leaching reaction, further improve the leaching rate and reduce energy consumption; please refer to Figure 2 and Figure 3In this embodiment, a circulation pipe 309, a circulation pump 3091 and a heat exchanger 3092 are added on the basis of the above embodiment; the circulation pipe 309 is connected to the combination barrel 3, and a circulation pump 3091 and a heat exchanger 3092 are provided on the circulation pipe 309. One end of the circulation pipe 309 is connected to the bottom end of the combination barrel 3, and the other end of the circulation pipe 309 is connected to the middle of the combination barrel 3. The heat medium inlet of the heat exchanger 3092 is connected to the heat medium of the cooling device 1203 through the heating pipe 3093. The cold medium outlet of the heat exchanger 3092 is connected to the circulating water pool 1106 through a return pipe 3096, a regulating pipe 3097 is connected between the heating pipe 3093 and the cooling water pipe 3094, and regulating valves 3098 are respectively provided on the regulating pipe 3097 and the cooling water pipe 3094. During leaching, the slurry in the combination barrel 3 is drawn out by the circulation pump 3091 and flows through the heat exchanger 3092 and then returns to the combination barrel 3. When flowing through the heat exchanger 3092, it exchanges heat with the hot water after heat exchange from the cooling device 1203 to heat the leached slurry. The cooling device 1203 is a cooling cylinder with an interlayer. The cooling water treated by the sewage treatment station 1105 and stored in the circulating water tank 1106 is passed into the interlayer of the cooling cylinder to cool the high-temperature manganese slag. At the same time, the cooling water is heated and then enters the heat exchanger 3092 to exchange heat with the leaching solution circulating from the combination barrel 3, thereby making full use of the heat of the high-temperature manganese slag and reducing energy consumption. The upper end of the ring tube 309 is connected to a distribution ring 3099, which surrounds the outer wall of the combining barrel 3. The distribution ring 3099 is provided with a number of branch pipes connected to the combining barrel 3. After the slurry is heated, it enters the inside of the combining barrel 3 from the periphery of the combining barrel 3 to ensure temperature balance. When the leaching reaction is just started, a large amount of heat is generated, and the slurry temperature may exceed 60°C. The water in the circulating water pool 1106 can be directly pumped to the heat exchanger 3092 through the regulating pipe 3097 to cool the slurry. The opening ratio of the regulating valve 3098 can be adjusted to ensure that the temperature during leaching is stable between 50°C and 60°C, thereby improving the leaching rate and reducing energy consumption.

[0046] Example 6

[0047] See also Figures 1 to 4 The method for producing electrolytic manganese metal disclosed in this embodiment uses the electrolytic manganese metal production line in Examples 1 to 5 to produce electrolytic manganese metal, comprising the following steps:

[0048] S1. Putting manganese ore into a crushing and grinding device 1 for powdering to obtain ore powder with a particle size of 85-100 meshes. The manganese ore is manganese carbonate ore, which is ground into ore powders with particle sizes of 85 meshes, 90 meshes, and 100 meshes.

[0049] S2, the mineral powder is weighed and put into the pulping barrel 2, and the anolyte stored in the anolyte storage tank 11 is added to the pulping barrel 2, and then stirred to mix the mineral powder and the anolyte into slurry.

[0050] S3, the slurry prepared in step S2 is pumped into the combination barrel 3, and the concentrated sulfuric acid stored in the sulfuric acid barrel 301 is added into the combination barrel 3 to adjust the pH value to between 1 and 3 for leaching reaction. The pH value is, for example, 1, 1.3, 2, 2.5, and 3. During the leaching reaction, the stirring device 308 is started for stirring. During stirring, the stirring blade 3084 on the stirring shaft 3083 stirs at the axis center of the combination barrel 3 at a speed of 200 r / min, and the stirring frame 3089 stirs in the reverse direction at the periphery of the stirring shaft 3083 at a speed of 100 r / min. Several flexible stirring belts 30811 are continuously shaken during rotation to form turbulent stirring, so that the slurry is mixed more evenly and the manganese leaching rate is improved. The manganese leaching rate can reach more than 95%.

[0051] S4. After 2-2.5 hours of leaching reaction, the manganese dioxide stored in the oxidant barrel 302 is added into the combining barrel 3 for oxidation reaction to oxidize the divalent iron ions in the leachate into trivalent iron ions. When the residual acid in the combining barrel 3 is 2-3 g / L, the anode mud at the bottom of the anode liquid storage tank 11 is added. The main component of the anode mud is manganese dioxide, so as to further improve the oxidation rate and recover the manganese in the anode mud.

[0052] S5. After the entire leaching reaction has lasted for 3 hours, the 15% ammonia water stored in the ammonia water barrel 303 is added into the combination barrel 3 for neutralization reaction, so that the pH value in the combination barrel 3 is adjusted to 6.0-6.5. At this time, the trivalent iron ions are completely hydrolyzed and precipitated, and most of the heavy metal ions are also hydrolyzed to form hydroxide precipitates.

[0053] S6, the slurry leached in step S5 is pumped to the first filter press 4 for filtration to obtain a primary filtrate and a primary filter residue; the primary filtrate is transported to the sulfidation tank 5 and the SDD agent stored in the sulfidation agent barrel 501 is added for sulfidation and impurity removal. After the heavy metals in the primary filtrate are qualified in the qualitative analysis, the second filter press 6 is used for solid-liquid separation to obtain a secondary filtrate and a secondary filter residue; the secondary filtrate enters the purification tank 7, and aluminum sulfate stored in the aluminum sulfate barrel 701 is added to the purification tank 7 to make the harmful impurities in the secondary filtrate condense and coarsen the particles and settle, and then the activated carbon stored in the activated carbon barrel 702 is added for adsorption and allowed to stand for 24 hours. The solution after adsorption and standing is sent to the third filter press 8 for fixed liquid separation to obtain a tertiary filtrate and a tertiary filter residue. The tertiary filtrate is a qualified electrolyte and is sent to the high-level tank 9 for electrolysis.

[0054] S7, the primary filter residue, secondary filter residue and tertiary filter residue in step S6 are sent to the manganese slag batching tank 1201, and the sulfur-fixing agent (lime) and heavy metal solidifying agent (heavy metal chelating agent) are added and stirred, and then sent to the low-temperature deammoniation section of the roasting kiln device 1202 for drying and deammoniation. The generated ammonia-containing high-humidity flue gas is precipitated and dust-removed by the first dust collector 1206 and then enters the condenser 1207 to condense into ammonia water, and the ammonia water is transported back to the ammonia water barrel 303, so as to effectively recycle the ammonia in the manganese slag; the manganese slag after deammoniation enters the high-temperature modification section for roasting, the roasting temperature is 950°C, and the residence time is 1 hour. The flue gas generated by the roasting enters the SNCR denitrification equipment 1208, the second dust removal equipment and the spray washing tower 1210 in turn for treatment, and the treated tail gas enters the second exhaust pipe 1211 for discharge, and the circulating liquid of the spray washing tower 1210 regularly enters the sedimentation tank 1212 for precipitation treatment to obtain a desulfurized gypsum product, which can be sold as a building material raw material.

[0055] S8. The calcined manganese slag is sent to the cooling device 1203 for cooling. The cooling device 1203 is a cooling cylinder with an interlayer. The interlayer of the cooling cylinder is passed through the cooling water treated by the sewage treatment station 1105 and stored in the circulating water pool 1106. The cooling water is heated and enters the heat exchanger 3092 to exchange heat with the leaching solution circulating from the combining barrel 3, so as to make full use of the waste heat of the manganese slag and ensure that the leaching temperature in the combining barrel 3 is stable between 50°C and 60°C.

[0056] S9. The cooled manganese slag is sent to the grinding device 1204 for grinding. The ground manganese slag powder is sent to the magnetic separation device 1205 to first select the iron product through the weak magnetic iron separation section, and then enter the strong magnetic manganese separation section to select the manganese product. The iron products are collected and sold to the outside, the manganese products are mixed with the mineral powder for re-leaching, and the remaining tailings are sold as building material raw materials, so as to make full use of the manganese slag resources and improve the economic benefits of the enterprise.

[0057] S10, add selenium dioxide stored in selenium dioxide barrel 901 to the high-level tank 9 in step S6, and then send the electrolyte in the high-level tank 9 to the electrolysis system 10 for electrolysis to prevent Mn 2+ Hydrolysis and improve current efficiency; after electrolysis, electrolytic manganese is precipitated on the cathode plate and sent to the post-processing integrated machine 1101 for passivation, cleaning, drying and peeling to obtain an electrolytic manganese product. The cathode plate after peeling is sent to the bubble plate tank 1103 and introduced into the anode liquid in the anode liquid storage tank 11 for soaking, so that the residual manganese is converted into manganese sulfate and removed. The cathode plate after soaking is sent to the cathode plate washing machine 1104 for washing, and the anode plate is sent to the anode plate washing machine 1102 for washing. The wastewater generated by washing is sent to the sewage treatment station 1105 for treatment. The washing water comes from the circulating water pool 1106, so as to realize the recycling of water resources and reduce the waste of water resources.

[0058] The above content is a further detailed description of the present invention in combination with specific / preferred embodiments, and it cannot be determined that the specific implementation of the present invention is limited to these descriptions. For ordinary technicians in the technical field to which the present invention belongs, without departing from the concept of the present invention, they can also make several substitutions or modifications to these described embodiments, and these substitutions or modifications should be regarded as belonging to the protection scope of the present invention. In the description of this specification, the description of reference terms "an embodiment", "some embodiments", "preferred embodiments", "examples", "specific examples" or "some examples" means that the specific features, structures, materials or characteristics described in combination with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily target the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In the absence of mutual contradiction, those skilled in the art can combine and combine the different embodiments or examples described in this specification and the features of different embodiments or examples. Although the embodiments of the present invention and their advantages have been described in detail, it should be understood that various changes, substitutions and modifications can be made herein without departing from the scope of protection of the patent application.

Claims

1. A production line for electrolytic manganese metal, characterized in that: The invention comprises a crushing and grinding device, a liquid preparation system, an electrolysis system, a post-processing system and a manganese slag treatment system, wherein the liquid preparation system comprises a pulping barrel, a chemical combination barrel, a first filter press, a sulfidation tank, a second filter press, a purification tank, a third filter press and a high-level tank, wherein the crushing and grinding device is connected to the pulping barrel, the pulping barrel outlet is connected to the chemical combination barrel, the chemical combination barrel is connected to the first filter press, the filtrate outlet of the first filter press is connected to the sulfidation tank, the sulfidation tank is connected to the second filter press, the filtrate outlet of the second filter press is connected to the purification tank, and the purification tank is connected to the third filter press. The chemical tank is connected with the third filter press, the filtrate outlet of the third filter press is connected with the high-level tank, the high-level tank is connected with the electrolysis system, the electrode plates after electrolysis by the electrolysis system are sent to the post-treatment system for treatment, the anolyte generated after electrolysis by the electrolysis system is sent to the anolyte storage tank through the return pipe, the liquid outlet of the anolyte storage tank is connected with the pulping barrel, the slag outlet of the anolyte storage tank is connected with the chemical combination barrel, and the filter residue outlets of the first filter press, the second filter press and the third filter press are connected to the manganese slag treatment system.

2. The electrolytic manganese production line according to claim 1, characterized in that: The combination barrel is connected to a sulfuric acid barrel, an oxidant barrel, an ammonia water barrel and an acid mist outlet pipe, the acid mist outlet pipe is connected in series with an acid mist absorption tower, an induced draft fan and a first chimney in sequence, the sulfidation pool is connected to a sulfiding agent barrel, the purification tank is connected to an aluminum sulfate barrel and an activated carbon barrel, and the high-level tank is connected to a selenium dioxide barrel.

3. The electrolytic manganese production line according to claim 2, characterized in that: The post-processing system includes a post-processing integrated machine, an anode plate rinser, a bubble plate tank, a cathode plate rinser, a sewage treatment station and a circulating water tank. The bubble plate tank is connected to the return liquid pipe, the anode plate rinser and the cathode plate rinser are connected to the sewage treatment station, and the circulating water tank is connected to the sewage treatment station. The cathode plate after electrolysis by the electrolysis system is sent to the post-processing integrated machine for treatment to obtain an electrolytic manganese product, and the anode plate is sent to the anode plate rinser for rinse treatment and reuse. The cathode plate treated by the post-processing integrated machine is sent to the bubble plate tank for immersion treatment and then sent to the cathode plate rinser for rinse treatment and reuse.

4. The electrolytic manganese production line according to claim 3, characterized in that: The manganese slag processing system includes a manganese slag batching tank, a roasting kiln device, a cooling device, a grinding device and a magnetic separation device. The manganese slag batching tank is connected to the inlet of the roasting kiln device, the inlet of the cooling device is connected to the outlet of the roasting kiln device, the outlet of the cooling device is connected to the inlet of the grinding device, and the inlet of the magnetic separation device is connected to the outlet of the grinding device.

5. The electrolytic manganese production line according to claim 4, characterized in that: The magnetic separation device comprises a weak magnetic iron separation section and a strong magnetic manganese separation section. The manganese slag powder passing through the weak magnetic iron separation section is used to select iron products, and the manganese slag powder passing through the strong magnetic manganese separation section is used to select manganese products.

6. The electrolytic manganese production line according to claim 5, characterized in that: The roasting kiln device includes a low-temperature deamination section and a high-temperature modification section. The flue gas outlet of the low-temperature deamination section is connected to the first dust collector, the outlet of the first dust collector is connected to the condenser, the liquid outlet of the condenser is connected to the ammonia water barrel, the flue gas outlet of the high-temperature modification section is connected to the SNCR denitrification equipment, the outlet of the SNCR denitrification equipment is connected to the second dust collector, the outlet of the second dust collector is connected to the spray washing tower, the flue gas outlet of the spray washing tower is connected to the second smoke exhaust pipe, and the washing liquid outlet of the spray washing tower is connected to the sedimentation tank.

7. The electrolytic manganese production line according to any one of claims 4 to 6, characterized in that: The combining barrel is provided with a stirring device, which includes a stirring motor, a speed reducer and a stirring shaft. The output end of the stirring motor is connected to the input end of the speed reducer, and the output end of the speed reducer is connected to one end of the stirring shaft. The stirring shaft extends from the top center of the combining barrel to the inside of the combining barrel. The stirring shaft is provided with a stirring blade. A center wheel is fixedly provided on the upper part of the stirring shaft, and the center wheel is meshedly connected with a planetary wheel. The planetary frame on the planetary wheel is fixed on the inner top wall of the combining barrel, and the outer periphery of the planetary wheel is meshedly connected with a gear ring. A stirring frame is connected to the gear ring, and the stirring frame is in contact with the inner side wall of the combining barrel. The bottom end of the stirring frame is rotatably sleeved on the lower part of the stirring shaft through a support ring, and a plurality of flexible stirring belts are vertically provided in the stirring frame.

8. The electrolytic manganese production line according to claim 7, characterized in that: The combination barrel is connected with a circulation pipe, on which a circulation pump and a heat exchanger are arranged, one end of the circulation pipe is connected with the bottom end of the combination barrel, and the other end of the circulation pipe is connected with the middle part of the combination barrel, the hot medium inlet of the heat exchanger is connected with the hot medium outlet of the cooling device through a heating pipe, the cold medium inlet of the cooling device is connected with the circulation water pool through a cooling water pipe, a cooling water pump is arranged on the cooling water pipe, and the cold medium outlet of the heat exchanger is connected with the circulation water pool through a return pipe, a regulating pipe is connected between the heating pipe and the cooling water pipe, and regulating valves are respectively arranged on the regulating pipe and the cooling water pipe.

9. The electrolytic manganese production line according to claim 8, characterized in that: The upper end of the circulation pipe is connected with a distribution ring, which surrounds and sleeves the outer wall of the combination barrel. The distribution ring is provided with a plurality of branch pipes connected with the inside of the combination barrel.

10. A method for producing electrolytic manganese metal, characterized in that: The production line of electrolytic manganese metal according to any one of claims 1 to 9 is used to produce electrolytic manganese metal, comprising the following steps: S1, putting the manganese ore into a crushing and grinding device for powdering to obtain ore powder with a particle size of 85-100 mesh; S2, measuring the mineral powder and putting it into the pulping barrel, adding the anode liquid stored in the anode liquid storage tank into the pulping barrel and stirring, so that the mineral powder and the anode liquid are mixed into a slurry; S3, conveying the slurry prepared in step S2 into a chemical combination barrel, adding concentrated sulfuric acid to carry out leaching reaction, and synchronously starting a stirring device for stirring, wherein the stirring blade stirs at the axis center of the chemical combination barrel, the stirring frame stirs in the reverse direction at the periphery of the stirring shaft, and the plurality of flexible stirring belts continuously shake during rotation; S4, adding manganese dioxide into the combination barrel for oxidation reaction, and adding the anode mud at the bottom of the anode liquid storage tank when the residual acid in the combination barrel is 2-3g / L; S5, adding 15% concentration of ammonia water into the combination barrel for neutralization reaction, so that the pH value in the combination barrel is adjusted to 6.0-6.5; S6, the slurry leached in step S5 is pumped to the first filter press for filtration to obtain a primary filtrate and a primary filter residue; the primary filtrate enters the sulfidation tank and is added with SDD agent for sulfidation and impurity removal, and after sulfidation, it is filtered by the second filter press to obtain a secondary filtrate and a secondary filter residue; the secondary filtrate enters the purification tank and is sequentially added with aluminum sulfate and activated carbon for adsorption and standing, and after adsorption and standing, it is filtered by the third filter press to obtain a tertiary filtrate and a tertiary filter residue, and the tertiary filtrate is sent to the high-level tank for electrolysis; S7, the primary filter residue, the secondary filter residue and the tertiary filter residue in step S6 are sent to the manganese slag batching tank, and the sulfur-fixing agent and the heavy metal solidifying agent are added and stirred, and then sent to the low-temperature deamination section of the roasting kiln device for drying and deamination. The flue gas generated in the low-temperature deamination section is precipitated and dusted by the first dust collector and then enters the condenser to condense into ammonia water, and the ammonia water is transported back to the ammonia water bucket; the manganese slag after deamination enters the high-temperature modification section for roasting, and the flue gas generated by the roasting enters the SNCR denitrification equipment, the second dust removal equipment and the spray washing tower in turn for treatment, and the treated tail gas enters the second exhaust pipe for external discharge, and the circulating liquid of the spray washing tower regularly enters the sedimentation tank for precipitation treatment to obtain a desulfurized gypsum product; S8, sending the manganese slag roasted in step S7 to a cooling device for heat exchange with the cooling water in the circulating water pool for cooling, and the cooling water is heated and then enters a heat exchanger for heat exchange with the leaching liquid circulating from the combination barrel, so as to make full use of the heat of the roasted manganese slag to ensure that the leaching temperature in the combination barrel is stable between 50°C and 60°C; S9, grinding the cooled manganese slag, sending the ground manganese slag powder into a magnetic separation device to sequentially select iron products and manganese products through a weak magnetic iron separation section and a strong magnetic manganese separation section, collecting the iron products and the remaining tailings and selling them externally, and blending the manganese products into the slurry in step S2; S10, add selenium dioxide to the electrolyte in the high-level tank in step S6 and send it to the electrolysis system for electrolysis. After electrolysis, electrolytic manganese metal is precipitated on the cathode plate and enters the post-processing integrated machine for treatment to obtain an electrolytic manganese metal product. The cathode plate after peeling off the product enters the bubble plate tank for soaking. The soaked cathode plate is sent to the cathode plate washing machine for washing, and the anode plate is sent to the anode plate washing machine for washing. The wastewater generated by washing is sent to the sewage treatment station for treatment.

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