A production apparatus and method for preparing manganese sulfate solution by reducing roasted manganese dioxide ore with ferrous sulfate.

Abstract

This invention relates to the field of comprehensive utilization of manganese resources and secondary resource utilization in non-ferrous metallurgy. Specifically, it provides a production apparatus and method for preparing manganese sulfate solution by reducing roasted manganese dioxide ore with ferrous sulfate. The production apparatus includes a manganese dioxide powder silo, a ferrous sulfate silo, a mixer, a mixed material silo, a reduction kiln, a post-treatment mechanism for the reduced roasted material, a reduced roasted material silo, a manganese sulfate dissolution leaching tank, a filter press, a hot water buffer tank, and a manganese sulfate leaching filter liquid storage tank, connected in sequence. The method for preparing manganese sulfate solution using the apparatus of this invention specifically includes: reducing roasting manganese dioxide by mixing ferrous sulfate and manganese dioxide ore, converting manganese dioxide into manganese sulfate under solid-phase conditions, and then obtaining manganese sulfate solution by hot water leaching. That is, this invention allows manganese sulfate to enter the liquid phase by water leaching alone without introducing external inorganic acids, thereby reducing production costs, reducing acid mist pollution, and reducing the cost and reaction time of acid addition reaction in the leaching process.

Description

Technical Field

[0001] This invention relates to the field of comprehensive utilization of manganese resources and secondary resource utilization in non-ferrous metallurgy, and particularly to a production apparatus and method for preparing manganese sulfate solution by reducing roasted manganese dioxide ore with ferrous sulfate. Background Technology

[0002] Manganese sulfate is an important chemical, with feed-grade and battery-grade manganese sulfate products having significant applications in multiple fields, such as: (1) Battery materials: used to produce ternary cathode (precursor) materials for lithium batteries, such as nickel-cobalt-manganese (NCM) ternary cathode materials and lithium manganese oxide; (2) Feed additives: manganese is one of the nine essential micronutrients (trace minerals) for healthy animals; (3) Agriculture: as a micronutrient fertilizer, it can be used as base fertilizer, seed soaking, seed dressing, top dressing, and foliar spraying to promote crop growth and increase yield; (4) Oxidizing agents: in batteries, manganese sulfate can act as an oxidizing agent to generate current; (5) Papermaking and ceramics: used as a raw material and manufacturing agent for papermaking, ceramics, printing and dyeing, ore flotation, electrolytic manganese, or as a raw material for other manganese salts. In summary, manganese sulfate products have significant application value in battery materials, animal and plant feed additives, papermaking and ceramics, and oxidizing agents. With the continuous advancement of science and technology and the ongoing development of industry, the applications of manganese sulfate products will continue to expand and deepen.

[0003] Existing industrial methods for preparing manganese sulfate solution from manganese dioxide ore mainly include reduction roasting-acid leaching and wet reduction leaching. In the reduction roasting-acid leaching method, manganese dioxide ore is typically roasted at high temperatures using reducing agents such as pulverized coal, followed by sulfuric acid leaching to obtain the manganese sulfate solution. This method generally suffers from high roasting temperatures, high acid consumption, severe acid mist, and difficulties in the comprehensive utilization of leaching residue. The wet reduction leaching method often uses ferrous salts or pyrite to reduce manganese dioxide under high-acid conditions, similarly resulting in high production costs and significant environmental impact. Both the reduction roasting-acid leaching and wet reduction leaching methods require the addition of sulfuric acid for high-temperature, high-acid leaching to obtain the manganese sulfate solution. However, this process suffers from long leaching times, high leaching costs, significant acid mist, and difficulties in selling the resulting leaching residue. Therefore, researching a device and method for preparing manganese sulfate solution without acid leaching is of positive significance for reducing production costs and acid mist pollution. Summary of the Invention

[0004] This invention provides a production apparatus and method for preparing manganese sulfate solution by reducing roasted manganese dioxide ore with ferrous sulfate. This production apparatus and method can introduce manganese sulfate into the liquid phase and obtain manganese sulfate solution by water leaching alone without introducing external inorganic acid, thereby reducing production costs and reducing acid mist pollution.

[0005] To achieve the above objectives, the technical solution of the present invention is as follows:

[0006] This invention provides a production apparatus for preparing manganese sulfate solution by reducing roasted manganese dioxide ore with ferrous sulfate, comprising:

[0007] Manganese dioxide powder silo;

[0008] Ferrous sulfate silo;

[0009] The mixer has its feed end connected to the discharge ends of the manganese dioxide powder silo and the ferrous sulfate silo, respectively.

[0010] A mixing silo, the feed end of which can introduce the mixture discharged from the mixer;

[0011] The reduction kiln has its feed end connected to the discharge end of the mixing silo;

[0012] The feed end of the reduction roasted material post-processing mechanism is connected to the discharge end of the reduction kiln;

[0013] The reduction roasting silo, with its inlet end and the outlet end of the reduction roasting post-processing mechanism, is used to store the post-processed reduction roasting material.

[0014] A manganese sulfate dissolution leaching tank is connected to the discharge end of the reduction roasting silo;

[0015] The filter press has its feed end connected to the manganese sulfate dissolution leaching tank via a leaching conveying pipe, and its cleaning water outlet connected to the manganese sulfate dissolution leaching tank via a rinsing filter liquid pipe, and is also equipped with a filter liquid outlet.

[0016] A hot water buffer tank is connected to the manganese sulfate dissolution leaching tank and the filter press via a first hot water delivery pipe and a second hot water delivery pipe, respectively.

[0017] The manganese sulfate leaching filtrate storage tank is connected to the filtrate outlet of the filter press via a manganese sulfate leaching filtrate pipeline.

[0018] Furthermore, it also includes a manganese dioxide powder pretreatment mechanism, which includes:

[0019] Crusher;

[0020] The manganese dioxide pre-conveying unit is located below the discharge end of the crusher;

[0021] A vertical grinding mill, the feed end of which is connected to the discharge end of the manganese dioxide powder conveying unit;

[0022] The manganese dioxide downstream conveying unit has its feed end connected to the discharge end of the vertical mill, and its discharge end connected to the feed end of the manganese dioxide powder silo. It is also equipped with a bag dust collector.

[0023] Furthermore, the manganese dioxide front conveying unit includes a belt conveyor and a manganese dioxide bucket elevator. The belt conveyor is located below the discharge end of the crusher, and the discharge end is connected to the feed end of the manganese dioxide bucket elevator. The discharge end of the manganese dioxide bucket elevator is connected to the vertical grinding mill.

[0024] Furthermore, the manganese dioxide post-conveying unit includes a manganese dioxide powder conveying pipe and a bag filter dust collector. The inlet end of the manganese dioxide powder conveying pipe is connected to the outlet end of the vertical mill and extends upward to connect with the inlet end of the bag filter dust collector. The ash hopper outlet of the bag filter dust collector is connected to the inlet end of the manganese dioxide powder silo.

[0025] Furthermore, the post-processing mechanism for the reduced roasted material includes:

[0026] The slag cooler has its feed end connected to the discharge end of the reduction kiln;

[0027] A ball mill, the feed end of which is connected to the discharge end of the slag cooler;

[0028] A vibrating screen is installed below the discharge end of the ball mill, and the discharge end is connected to the feed end of the reduction roasting powder bucket elevator and the reduction roasting silo.

[0029] Furthermore, the manganese sulfate dissolution leaching tank is equipped with a stirring device.

[0030] Furthermore, the manganese dioxide powder silo and the ferrous sulfate silo are located above the mixer;

[0031] And / or, a mixing screw feeder and a mixing bucket elevator are provided between the mixer and the mixing silo, the feed end of the mixing screw feeder is located below the mixer, the discharge end of the mixing screw feeder is located above the feed end of the mixing bucket elevator, and the discharge end of the mixing bucket elevator extends upward to the top of the mixing silo.

[0032] And / or, the mixing silo is located on one side of the ferrous sulfate silo, and a reduction kiln and a reduction roasting post-processing mechanism are arranged in sequence below it;

[0033] And / or, the reduction roasting silo is located above the manganese sulfate dissolution leaching tank.

[0034] Another aspect of the present invention provides a method for preparing manganese sulfate solution using the production apparatus described above, comprising the following steps:

[0035] S1. Manganese dioxide ore is processed to obtain manganese dioxide ore powder, which is stored in the manganese dioxide powder silo. The mesh size of the manganese dioxide ore powder is not less than 100 mesh, and the proportion between 100 mesh and 150 mesh reaches more than 95%.

[0036] S2. Ferrous sulfate is stored in the ferrous sulfate silo. The manganese dioxide powder and ferrous sulfate in the manganese dioxide powder silo and the ferrous sulfate silo are introduced into the mixer at a manganese-sulfur ratio of 120-150:100. The powder is mixed evenly to obtain a mixture of ferrous sulfate and manganese dioxide.

[0037] S3. The mixture of ferrous sulfate and manganese dioxide is introduced into the mixing silo and then into the reduction kiln. The mixture is reduced and roasted at 650-780℃ for 100-150 minutes to obtain the roasted manganese sulfate and ferric oxide products.

[0038] S4. The calcined products of manganese sulfate and ferric oxide are cooled and ground by the post-processing mechanism of the reduced calcined material to obtain a mixed powder of manganese sulfate and ferric oxide. The mixed powder of manganese sulfate and ferric oxide has a mesh size of not less than 120 mesh, and the proportion of 120 mesh to 200 mesh is more than 95.00%.

[0039] S5. The mixed powder of manganese sulfate and ferric oxide is introduced into the reduction roasting silo, and then introduced into the manganese sulfate dissolution leaching tank through the reduction roasting silo. Hot water or washing water of the leaching residue is added at a liquid-solid ratio of 1.9-3:1 for dissolution and leaching. The leaching temperature is controlled at 80-90℃ and the time is 3-4 hours. After dissolution and leaching are completed, the primary filter residue and primary filtrate are separated by a filter press. The primary filtrate is manganese sulfate solution and the primary filter residue is ferric oxide filter residue.

[0040] Furthermore, step S6 involves adding hot water to the ferric oxide filter residue in a filter press at a liquid-to-solid ratio of 1.9-3:1 for rinsing. The rinsing temperature is controlled at 60-80℃, and the rinsing time is 0.8-2 hours. After rinsing, the secondary filter residue and secondary filtrate are separated by a filter press. The obtained secondary filter residue is the ferric oxide product, and the obtained secondary filtrate is the washing water for the leaching residue. This is then returned to step S5 for dissolution and leaching.

[0041] Furthermore, the manganese dioxide ore powder A1 and ferrous sulfate are mixed at a manganese-sulfur ratio of 135:100.

[0042] The production apparatus and method described above for preparing manganese sulfate solution by reducing roasted manganese dioxide ore with ferrous sulfate can achieve the conversion of manganese dioxide into manganese sulfate under solid-phase conditions by using ferrous sulfate as a roasting reducing agent and mixing it with manganese dioxide ore for reduction roasting. Then, the manganese sulfate solution is obtained by hot water leaching. That is, without introducing external inorganic acid, manganese sulfate can enter the liquid phase by water leaching alone, thereby reducing production costs, reducing acid mist pollution, reducing the cost and reaction time of acid addition reaction in the leaching process, avoiding the impact of acid mist generated during the leaching process on personnel and the environment, and achieving a reduction rate of manganese dioxide of over 96% and a leaching rate of manganese sulfate of over 95%. After impurity removal and crystallization, it can be used to produce feed-grade manganese sulfate products and battery-grade manganese sulfate products.

[0043] Meanwhile, during the roasting process, ferrous sulfate is converted into iron oxide with Fe2O3 as the main phase. After leaching to prepare manganese sulfate solution, the remaining filter residue is mainly Fe2O3, and the Fe2O3 content of the product reaches more than 80%, which can be sold directly, giving it the advantage of easy sales of filter residue.

[0044] This invention, through the rational design and layout of the production equipment, enables a streamlined production process from crushing manganese dioxide ore, mixing with ferrous sulfate, roasting, and leaching. It also includes appropriate turnover silos, such as mixing silos and reduction roasting silos, allowing for a rational arrangement of the production process. The mixing, roasting, and leaching processes can be carried out simultaneously, shortening the production cycle, improving production efficiency, reducing equipment energy consumption, and thus better improving product profits.

[0045] The calcining reducing agent ferrous sulfate used in this invention can be a byproduct of industrial production, such as ferrous sulfate heptahydrate, a byproduct of titanium dioxide production. The raw material price is very low, which can further reduce the production cost of the product and increase the product profit.

[0046] In summary, this invention has advantages such as low-cost reducing agent, reasonable production equipment layout, low production cost, short production process, high product profit, and easy sale of leaching residue. Furthermore, by reducing the roasted manganese dioxide ore with ferrous sulfate, the roasted material can be further purified and crystallized by dissolving the manganese sulfate solution obtained from leaching to produce feed-grade and battery-grade manganese sulfate products. The leaching residue is then washed by a rinsing device to obtain ferric oxide products with a content of over 80%, thus achieving the goal of maximizing the resource utilization and profitability of ferrous sulfate and manganese dioxide ore. Attached Figure Description

[0047] Figure 1 This is a schematic diagram of the structure of an embodiment of the production apparatus of the present invention.

[0048] Figure 2 This is a schematic diagram of the process for preparing manganese sulfate solution according to an example of the present invention.

[0049] 1-Crusher, 2-Belt Conveyor, 3-Manganese Dioxide Hopper Elevator, 4-Vertical Grinding Mill, 5-Bag Collector, 6-Rotary Feeder Valve, 7-Manganese Dioxide Powder Silo, 8-Ferrous Sulfate Silo, 9-Manganese Dioxide Powder Feeder, 10-Ferrous Sulfate Feeder, 11-Mixer, 12-Mixed Material Screw Feeder, 13-Mixed Material Hopper Elevator, 14-Mixed Material Silo, 15-Mixed Material Feeder Valve, 16-Reduction Kiln, 17-Slag Cooler 18-Ball mill, 19-Vibrating screen, 20-Reduction roasting powder bucket elevator, 21-Reduction roasting silo, 22-Reduction roasting feeder, 23-Manganese sulfate dissolution leaching tank, 24-Leaching conveying pipeline, 25-Filter press, 26-Hot water buffer tank, 27-First hot water conveying pipeline, 28-Manganese sulfate leaching filtrate pipeline, 29-Manganese sulfate leaching filtrate storage tank, 30-Rinsing filtrate pipeline, 31-Second hot water conveying pipeline. Detailed Implementation

[0050] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0051] In the description of this invention, it should be noted that the terms "upper" and "lower" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship in which the product of this invention is usually placed when in use. They are only used to facilitate the description of this invention and to simplify the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0052] In this application, unless otherwise expressly specified and limited, the terms "installation," "connection," "joining," "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0053] Example 1

[0054] This embodiment provides a production apparatus for preparing manganese sulfate solution by reducing roasted manganese dioxide ore with ferrous sulfate, such as... Figure 1As shown, the system includes a manganese dioxide powder silo 7, a ferrous sulfate silo 8, a mixer 11, a mixing silo 14, a reduction kiln 16, a reduction roasting feed post-processing unit, a reduction roasting feed silo 21, a manganese sulfate dissolution leaching tank 23, a filter press 25, a hot water buffer tank 26, and a manganese sulfate leaching filter liquid storage tank 29. Specifically: the manganese dioxide powder silo 7 is used to store pulverized manganese dioxide ore powder, and the ferrous sulfate silo 8 is used to store ferrous sulfate powder; the mixer 11 has its inlet connected to the outlets of both the manganese dioxide powder silo 7 and the ferrous sulfate silo 8, meaning the mixer 11 receives manganese dioxide ore powder from the manganese dioxide powder silo 7 and ferrous sulfate powder from the ferrous sulfate silo 8, and then mixes them evenly; the mixing silo 14 has an inlet that can draw... The mixture discharged from the mixer 11 (i.e., the mixture of ferrous sulfate and manganese dioxide) can be temporarily stored in the mixing silo 14 and will proceed to the next process according to instructions when needed. The reduction kiln 16, with its feed end connected to the discharge end of the mixing silo 14, allows the mixture from the mixing silo 14 to enter the reduction kiln 16 for reduction roasting. After roasting, the ferrous sulfate and manganese dioxide yield reduced roasted material (i.e., the roasted product of manganese sulfate and ferric oxide). The reduced roasted material post-processing mechanism, with its feed end connected to the discharge end of the reduction kiln 16, allows the reduced roasted material after roasting in the reduction kiln 16 to undergo post-processing, such as cooling and pulverizing. The reduced roasted material silo 21, with its feed end connected to the discharge end of the reduced roasted material post-processing mechanism, is used for storage. The reduced roasted feed (i.e., a mixture of manganese sulfate and ferric oxide powder) is stored in the reduced roasted feed silo 21, which is mainly used for the transfer of the reduced roasted feed after post-processing. When needed, it enters the next process according to instructions. The manganese sulfate dissolution leaching tank 23 is connected to the discharge end of the reduced roasted feed silo 21. The reduced roasted feed stored in the reduced roasted feed silo 21 enters the manganese sulfate dissolution leaching tank 23, and a mixed liquid with leaching residue is obtained by hot water immersion. The filter press 25 is connected to the manganese sulfate dissolution leaching tank 23 through the leaching conveying pipe 24. The mixed liquid with leaching residue is separated into primary filtrate and leaching residue by the filter press 25. After separation, the leaching residue is washed with water. After washing, it is filtered again to separate the secondary filtrate. The filter press 25 consists of a manganese sulfate solution and a secondary filter residue. The secondary filter residue is ferric oxide. The washing water outlet is connected to the manganese sulfate dissolution leaching tank 23 via the rinsing filtrate pipe 30. The secondary filtrate (washing water for the leaching residue) can be returned to the manganese sulfate dissolution leaching tank 23 to soak the treated reduced roasted material. The filter press 25 is equipped with a filter outlet to discharge the primary filtrate, which is the manganese sulfate solution. A hot water buffer tank 26 is connected to the manganese sulfate dissolution leaching tank 23 and the filter press 25 via a first hot water delivery pipe 27 and a second hot water delivery pipe 31. The hot water buffer tank 26 provides hot water to the manganese sulfate dissolution leaching tank 23 and the filter press 25 to soak the treated reduced roasted material and wash the leaching residue.The manganese sulfate leaching filtrate storage tank 29 is connected to the filtrate outlet of the filter press 25 via a manganese sulfate leaching filtrate pipeline 28, for storing and circulating the primary filtrate (i.e., manganese sulfate solution). The above-described production apparatus for preparing manganese sulfate solution by reducing and roasting manganese dioxide ore with ferrous sulfate can complete the entire process from mixing and roasting manganese dioxide ore powder with ferrous sulfate, followed by hot water leaching to obtain manganese sulfate solution.

[0055] Furthermore, this embodiment further improves the production device for processing manganese dioxide ore into manganese dioxide powder, to further realize fully automated production. Specifically, it also includes a manganese dioxide powder pretreatment mechanism, which includes a crusher 1, a manganese dioxide pre-conveyor unit, and a vertical grinding mill 4. The crusher 1 is used for preliminary crushing of the manganese dioxide ore. For the requirements of subsequent processing in this embodiment, it is preferable to crush the manganese dioxide ore to a particle size smaller than 80mm, with more than 80% of the particles smaller than 50mm. The manganese dioxide pre-conveyor unit is located below the discharge end of the crusher 1. The vertical grinding mill... 4. Its feed end is connected to the discharge end of the manganese dioxide powder conveying unit. The crushed manganese dioxide ore is conveyed to the vertical mill 4 for crushing through the manganese dioxide pre-conveying unit. In this embodiment, in order to better mix and contact with ferrous sulfate, the mesh size of the obtained manganese dioxide ore powder is preferably not less than 100 mesh, and the proportion between 100 mesh and 150 mesh reaches more than 95%. The manganese dioxide post-conveying unit has its feed end connected to the discharge end of the vertical mill 4 and its discharge end connected to the feed end of the manganese dioxide powder silo 7. It is also equipped with a bag dust collector 5. The bag dust collector 5 can quickly capture manganese dioxide ore powder and reduce dust pollution in the workshop.

[0056] This embodiment further provides a preferred structure for the manganese dioxide pre-conveyor unit, which includes a belt conveyor 2 and a manganese dioxide bucket elevator 3. The belt conveyor 2 is located below the discharge end of the crusher 1, and the discharge end is connected to the feed end of the manganese dioxide bucket elevator 3. The discharge end of the manganese dioxide bucket elevator 3 is connected to the vertical grinding mill 4.

[0057] Meanwhile, this embodiment further provides a preferred structure for the manganese dioxide post-conveying unit, which includes a manganese dioxide powder conveying pipe and a bag dust collector 5. The inlet end of the manganese dioxide powder conveying pipe is connected to the outlet end of the vertical mill 4 and extends upward to connect with the inlet end of the bag dust collector 5. The ash hopper outlet of the bag dust collector 5 is connected to the inlet end of the manganese dioxide powder silo 7.

[0058] The layout of the aforementioned manganese dioxide pre-conveying unit and manganese dioxide post-conveying unit is designed to better meet the requirements of the workshop layout. Given the large weight and volume of manganese dioxide ore, to better feed it into crusher 1 and to better avoid the impact of crushing vibrations on subsequent equipment, it is separately located in a lower space. The manganese dioxide pre-conveying unit is not connected to crusher 1 via pipelines, but instead uses belt conveyor 2 to transport the crushed manganese dioxide ore. After being transported by belt conveyor 2, it is then lifted by manganese dioxide bucket elevator 3 and transported to vertical grinding mill 4. Vertical grinding mill 4 is located on one side of crusher 1. After grinding by vertical grinding mill 4, the negative pressure of bag filter dust collector 5 is used to lift the manganese dioxide ore powder upwards, raising it to a higher height so that it can subsequently fall into manganese dioxide powder silo 7 by gravity.

[0059] This embodiment further provides a preferred structure for the post-processing mechanism of the reduction roasted feedstock. The post-processing mechanism includes a slag cooler 17, a ball mill 18, and a vibrating screen 19. Specifically: the slag cooler 17 has its feed end connected to the discharge end of the reduction kiln 16. The reduction roasted feedstock after roasting in the reduction kiln 16 enters the slag cooler 17 for cooling, thus improving the turnover efficiency of the reduction kiln 16 and allowing the reduction kiln to maintain a continuous roasting temperature, reducing fuel consumption; the ball mill 18 has its feed end connected to the discharge end of the slag cooler 17, and the cooled reduction roasted feedstock is fed into the ball mill 19. The calcined material is ball-milled into powder to improve the leaching efficiency of manganese sulfate. To ensure the leaching rate of manganese sulfate, in this embodiment, the mesh size of the cooled reduced calcined material after ball milling is preferably not less than 120 mesh, and the proportion between 120 mesh and 200 mesh reaches more than 95.00%. The vibrating screen 19 is set below the discharge end of the ball mill 18, and the discharge end is connected to the feed end of the reduced calcined material hopper elevator 20 and the reduced calcined material silo 21. The vibrating screen 19 can ensure that the mesh size of the post-processed reduced calcined material meets the requirements.

[0060] Furthermore, the manganese sulfate dissolution leaching tank 23 is equipped with a stirring device, which can better ensure the leaching efficiency of manganese sulfate.

[0061] Furthermore, this embodiment rationally arranges the various devices to better optimize the layout of the production unit within a limited space. Simultaneously, powder from some devices can fall to the next device under gravity, reducing energy consumption. Specifically, the baghouse dust collector 5 is positioned above the manganese dioxide powder silo 7. The manganese dioxide powder silo 7 and the ferrous sulfate silo 8 are located above the mixer 11 and on one side of the vertical mill 4. A valve is installed in the pipeline between the baghouse dust collector 5 and the manganese dioxide powder silo 7 for periodic feeding; in this embodiment, a star-shaped feeder valve 6 is used. The pipelines between the manganese dioxide powder silo 7, the ferrous sulfate silo 8, and the mixer 11 are also equipped with manganese dioxide powder feeders 9 and ferrous sulfate feeders 10, or valves, respectively, to meet the requirements of periodic and batch feeding. A mixing screw feeder 12 and a mixing bucket elevator 13 are installed between the mixer 11 and the mixing silo 8. The feed end of the mixing screw feeder 12 is located below the mixer 11, and the discharge end of the mixing screw feeder 12 is located above the feed end of the mixing bucket elevator 13. The discharge end of the mixing bucket elevator 13 extends upward to the top of the mixing silo 8. The mixing silo 14 is located on one side of the ferrous sulfate silo 8, and a reduction kiln 16 and a reduction roasting post-processing mechanism are arranged below it in sequence. The mixture in the mixing silo 14 can enter the reduction kiln 16 by gravity. To meet the requirements of periodic feeding, a mixing feed valve 15 is installed in the pipeline between the mixing silo 14 and the reduction kiln 16. After the reduction roasting is completed in the reduction kiln 16, the reduction roasted material can enter the slag cooler 17, the ball mill 18 and the vibrating screen 19 in sequence by gravity. The post-processed reduction roasted material is lifted to the reduction roasted material silo 21 by the reduction roasted material powder bucket elevator 20. The reduction roasted material silo 21 is located above the manganese sulfate dissolution leaching tank 23. The post-processed reduction roasted material can enter the manganese sulfate dissolution leaching tank 23 by gravity. In order to meet the requirements of periodic and batch feeding, a reduction roasted material feeder 22 is set between the manganese sulfate dissolution leaching tank 23 and the manganese sulfate dissolution leaching tank 23.

[0062] Additionally, the filter press 25 is located above the manganese sulfate dissolution leaching tank 23 to facilitate the introduction of the filtrate into the manganese sulfate leaching filtrate storage tank 29. Therefore, a pump is installed in the leaching delivery pipeline to introduce the mixed liquid containing leaching residue from the manganese sulfate dissolution leaching tank 23 into the filter press 25. A pump is also installed at the outlet of the hot water buffer tank to introduce hot water into the first hot water delivery pipeline 27 or the second hot water delivery pipeline 31. Valves are installed in the first hot water delivery pipeline 27, the second hot water delivery pipeline 31, the rinsing filtrate pipeline 30, the leaching delivery pipeline 24, and the rinsing filtrate pipeline 30 to open or close at appropriate process nodes.

[0063] Example 2

[0064] This embodiment provides a method for preparing manganese sulfate solution using the above-mentioned production apparatus, including the following steps:

[0065] S1. Manganese dioxide ore is processed to obtain manganese dioxide ore powder, which is stored in manganese dioxide powder silo 7. The mesh size of the manganese dioxide ore powder is not less than 100 mesh, and the proportion between 100 mesh and 150 mesh reaches more than 95%.

[0066] S2. Ferrous sulfate is stored in ferrous sulfate silo 8. Manganese dioxide powder and ferrous sulfate from manganese dioxide powder silo 7 and ferrous sulfate silo 8 are introduced into mixer 11 at a manganese-sulfur ratio of 120-150:100 (e.g., 120:100, 135:100, 140:100 or 150:100) to mix the powder evenly and obtain a mixture of ferrous sulfate and manganese dioxide.

[0067] S3. The mixture of ferrous sulfate and manganese dioxide is introduced into the mixing silo 14 and then into the reduction kiln 16. The mixture is reduced and roasted at 650-780℃ (e.g., 650℃, 700℃, 725℃, 750℃ or 780℃) for 100-150 min (e.g., 100 min, 120 min, 145 min or 150 min) to obtain the roasted manganese sulfate and ferric oxide products.

[0068] S4. The calcined products of manganese sulfate and ferric oxide are cooled and ground by a post-processing unit for reducing calcined materials to obtain a mixed powder of manganese sulfate and ferric oxide. The mesh size of the mixed powder of manganese sulfate and ferric oxide is not less than 120 mesh, and the proportion between 120 mesh and 200 mesh reaches more than 95.00%.

[0069] S5. Introduce the mixed powder of manganese sulfate and ferric oxide into the reduction roasting silo 21, and then introduce it into the manganese sulfate dissolution leaching tank 23 through the reduction roasting silo 21. Add hot water or washing water of the leaching residue at a liquid-solid ratio of 1.9-3:1 (e.g., 1.9:1, 2:1, 2.5:1 or 3:1) for dissolution leaching. Control the leaching temperature at 80-90℃ (e.g., 80℃, 85℃, 88℃ or 90℃) for 3-4 hours (e.g., 3 hours, 3.2 hours, 3.5 hours or 4 hours). After dissolution leaching is completed, separate the primary filter residue and primary filtrate through the filter press 25. The primary filtrate is manganese sulfate solution, and the primary filter residue is ferric oxide filter residue.

[0070] S6. The ferric oxide filter residue is rinsed in a filter press with hot water at a liquid-to-solid ratio of 1.9-3:1 (e.g., 1.9:1, 2:1, 2.5:1 or 3:1). The rinsing temperature is controlled at 60-80℃ (e.g., 60℃, 70℃, 75℃ or 80℃), and the rinsing time is 0.8-2h (e.g., 0.8h, 1.2h, 1.5h or 2h). After rinsing, the secondary filter residue and secondary filtrate are separated by filter press 25. The obtained secondary filter residue is the ferric oxide product, and the obtained secondary filtrate is the washing water for the leaching residue. It is returned to step S5 for dissolution and leaching.

[0071] The method of the present invention will be further described below by way of examples, but the scope of protection of the present invention is not limited to these embodiments.

[0072] Example 2-1

[0073] The manganese dioxide ore used in this embodiment comes from Gabon's high-iron manganese dioxide ore, with a manganese content of 42.00%, a manganese dioxide content of 65.33%, and an iron content of 15.80%; the ferrous sulfate heptahydrate used is a by-product of ferrous sulfate produced by a titanium dioxide manufacturer in Guangxi, with a ferrous sulfate heptahydrate content of 90.00%.

[0074] A method for preparing manganese sulfate solution by reducing roasted manganese dioxide ore with ferrous sulfate includes the following steps:

[0075] S1. Manganese dioxide ore is processed to obtain manganese dioxide ore powder, which is stored in manganese dioxide powder silo 7. The mesh size of the manganese dioxide ore powder is not less than 100 mesh, and the proportion between 100 mesh and 150 mesh reaches 96.33%.

[0076] S2. Ferrous sulfate is stored in ferrous sulfate silo 8. Manganese dioxide powder and ferrous sulfate from manganese dioxide powder silo 7 and ferrous sulfate silo 8 are introduced into mixer 11 at a manganese-sulfur ratio of 135:100. The powder is mixed evenly to obtain a mixture of ferrous sulfate and manganese dioxide.

[0077] S3. The mixture of ferrous sulfate and manganese dioxide is introduced into the mixing silo 14, and then fed into the reduction kiln 16 through the mixing silo 14. It is then reduced and roasted at 700℃ for 120 minutes to obtain the roasted manganese sulfate and ferric oxide products. The total manganese content of the roasted manganese sulfate and ferric oxide products is 20.826%, the divalent manganese content is 20.11%, the total iron content is 32.9%, and the reduction rate of manganese dioxide ore reaches 96.55%.

[0078] S4. The calcined products of manganese sulfate and ferric oxide are cooled and ground by a post-processing unit for reducing calcined materials to obtain a mixed powder of manganese sulfate and ferric oxide. The mesh size of the mixed powder of manganese sulfate and ferric oxide is not less than 120 mesh, and the proportion between 120 mesh and 200 mesh reaches 96.70%.

[0079] S5. The mixed powder of manganese sulfate and ferric oxide is introduced into the reduction roasting silo 21, and then introduced into the manganese sulfate dissolution leaching tank 23 through the reduction roasting silo 21. Hot water or washing water of the leaching residue is added at a liquid-to-solid ratio of 2:1 for dissolution and leaching. The leaching temperature is controlled at 85℃, and the dissolution and leaching time is 3 hours. The manganese sulfate dissolution and leaching rate reaches 95.12%. After the dissolution and leaching is completed, the primary filter residue and primary filtrate are separated by a filter press 25. The primary filtrate is a manganese sulfate solution with a manganese concentration of 101.28 g / L. The primary filter residue is ferric oxide filter residue. The iron content of the obtained ferric oxide filter residue reaches 59.32%.

[0080] S6. Add hot water to the ferric oxide filter residue in the filter press at a liquid-to-solid ratio of 2:1 for rinsing. The rinsing temperature is controlled at 70℃ and the rinsing time is 1 hour. After rinsing, separate the secondary filter residue and secondary filtrate through the filter press 25. The obtained secondary filter residue is the ferric oxide product with a content of 86.06%. The obtained secondary filtrate is the washing water for the leaching residue and is returned to step S5 for dissolution and leaching.

[0081] S7. After further impurity removal and crystallization of the manganese sulfate filtrate obtained in step S5, feed-grade manganese sulfate product is obtained. The main content of the obtained feed-grade manganese sulfate product reaches 98.07%, and all indicators of feed-grade manganese sulfate content meet the qualification requirements.

[0082] The reduction rate of manganese dioxide ore obtained by this process reached 96.55%, the dissolution and leaching rate of manganese sulfate reached 95.12%, the manganese content of the manganese sulfate solution reached 101.28 g / L, the content of ferric oxide product reached 86.06%, and the content of feed-grade manganese sulfate product reached 98.07%. All other indicators met the qualification requirements for feed-grade manganese sulfate.

[0083] Example 2-2

[0084] The high-iron manganese dioxide ore used in this embodiment comes from South African manganese dioxide ore, with a manganese content of 43.55%, a manganese dioxide content of 66.79%, and an iron content of 14.99%; the ferrous sulfate heptahydrate used is a by-product of ferrous sulfate produced by a Chongqing titanium dioxide manufacturer, with a ferrous sulfate heptahydrate content of 95.00%.

[0085] A method for preparing manganese sulfate solution by reducing roasted manganese dioxide ore with ferrous sulfate includes the following steps:

[0086] S1. Manganese dioxide ore is processed to obtain manganese dioxide ore powder, which is stored in manganese dioxide powder silo 7. The mesh size of the manganese dioxide ore powder is not less than 100 mesh, and the proportion between 100 mesh and 150 mesh reaches 95.02%.

[0087] S2. Ferrous sulfate is stored in ferrous sulfate silo 8. Manganese dioxide powder and ferrous sulfate from manganese dioxide powder silo 7 and ferrous sulfate silo 8 are introduced into mixer 11 at a manganese-sulfur ratio of 135:100. The powder is mixed evenly to obtain a mixture of ferrous sulfate and manganese dioxide.

[0088] S3. The mixture of ferrous sulfate and manganese dioxide is introduced into the mixing silo 14, and then fed into the reduction kiln 16 through the mixing silo 14. It is then reduced and roasted at 750℃ for 120 minutes to obtain the roasted manganese sulfate and ferric oxide products. The total manganese content of the roasted manganese sulfate and ferric oxide products is 23.19%, the divalent manganese content is 22.32%, the total iron content is 31.13%, and the reduction rate of manganese dioxide ore reaches 96.25%.

[0089] S4. The calcined products of manganese sulfate and ferric oxide are cooled and ground by a post-processing unit for reducing calcined materials to obtain a mixed powder of manganese sulfate and ferric oxide. The mesh size of the mixed powder of manganese sulfate and ferric oxide is not less than 120 mesh, and the proportion between 120 mesh and 200 mesh reaches 95.22%.

[0090] S5. The mixed powder of manganese sulfate and ferric oxide is introduced into the reduction roasting silo 21, and then introduced into the manganese sulfate dissolution leaching tank 23 through the reduction roasting silo 21. Hot water or washing water of the leaching residue is added at a liquid-to-solid ratio of 2:1 for dissolution and leaching. The leaching temperature is controlled at 85℃, and the dissolution and leaching time is 3 hours. The manganese sulfate dissolution and leaching rate reaches 95.01%. After dissolution and leaching is completed, the primary filter residue and primary filtrate are separated by a filter press 25. The primary filtrate is a manganese sulfate solution with a manganese concentration of 111.20 g / L. The primary filter residue is ferric oxide filter residue. The iron content of the obtained ferric oxide filter residue reaches 58.91%.

[0091] S6. Add hot water to the ferric oxide filter residue in the filter press at a liquid-to-solid ratio of 2:1 for rinsing. The rinsing temperature is controlled at 73℃ and the rinsing time is 1 hour. After rinsing, separate the secondary filter residue and secondary filtrate through the filter press 25. The obtained secondary filter residue is the ferric oxide product with a content of 84.35%. The obtained secondary filtrate is the washing water for the leaching residue and is returned to step S5 for dissolution and leaching.

[0092] S7. After further impurity removal and crystallization of the manganese sulfate filtrate obtained in step S5, feed-grade manganese sulfate product is obtained. The main content of the obtained feed-grade manganese sulfate product reaches 98.16%, and all indicators of feed-grade manganese sulfate content meet the qualification requirements.

[0093] The reduction rate of manganese dioxide ore obtained by this process reached 96.25%, the dissolution and leaching rate of manganese sulfate reached 95.01%, the manganese content of the manganese sulfate solution reached 111.20 g / L, the content of ferric oxide product reached 84.35%, and the content of feed-grade manganese sulfate product reached 98.16%. All other indicators met the qualification requirements for feed-grade manganese sulfate.

[0094] Example 2-3

[0095] The manganese dioxide ore used in this embodiment is from Australian manganese dioxide ore, with a manganese content of 43.72%, a manganese dioxide content of 69.09%, and an iron content of 11.88%; the ferrous sulfate heptahydrate used is a ferrous sulfate product produced by Henan Huiyi Hai Environmental Protection Technology Co., Ltd., with a ferrous sulfate heptahydrate content of 99.00%.

[0096] A method for preparing manganese sulfate solution by reducing roasted manganese dioxide ore with ferrous sulfate includes the following steps:

[0097] S1. Manganese dioxide ore is processed to obtain manganese dioxide ore powder, which is stored in manganese dioxide powder silo 7. The mesh size of the manganese dioxide ore powder is not less than 100 mesh, and the proportion between 100 mesh and 150 mesh reaches 95.86%.

[0098] S2. Ferrous sulfate is stored in ferrous sulfate silo 8. Manganese dioxide powder and ferrous sulfate from manganese dioxide powder silo 7 and ferrous sulfate silo 8 are introduced into mixer 11 at a manganese-sulfur ratio of 135:100. The powder is mixed evenly to obtain a mixture of ferrous sulfate and manganese dioxide.

[0099] S3. The mixture of ferrous sulfate and manganese dioxide is introduced into the mixing silo 14, and then fed into the reduction kiln 16 through the mixing silo 14. It is then reduced and roasted at 730℃ for 120 minutes to obtain the roasted manganese sulfate and ferric oxide products. The total manganese content of the roasted manganese sulfate and ferric oxide products is 24.71%, the divalent manganese content is 24.17%, the total iron content is 30.61%, and the reduction rate of manganese dioxide ore reaches 97.83%.

[0100] S4. The calcined products of manganese sulfate and ferric oxide are cooled and ground by a post-processing unit for reducing calcined materials to obtain a mixed powder of manganese sulfate and ferric oxide. The mesh size of the mixed powder of manganese sulfate and ferric oxide is not less than 120 mesh, and the proportion between 120 mesh and 200 mesh reaches 95.81%.

[0101] S5. The mixed powder of manganese sulfate and ferric oxide is introduced into the reduction roasting silo 21, and then introduced into the manganese sulfate dissolution leaching tank 23 through the reduction roasting silo 21. Hot water or washing water of the leaching residue is added at a liquid-to-solid ratio of 2:1 for dissolution and leaching. The leaching temperature is controlled at 90℃, and the dissolution and leaching time is 4 hours. The manganese sulfate dissolution and leaching rate reaches 96.55%. After the dissolution and leaching is completed, the primary filter residue and primary filtrate are separated by a filter press 25. The primary filtrate is a manganese sulfate solution with a manganese concentration of 115.21 g / L. The primary filter residue is ferric oxide filter residue. The iron content of the obtained ferric oxide filter residue reaches 56.69%.

[0102] S6. Add hot water to the ferric oxide filter residue in the filter press at a liquid-to-solid ratio of 2:1 for rinsing. The rinsing temperature is controlled at 70℃ and the rinsing time is 1 hour. After rinsing, separate the secondary filter residue and secondary filtrate through the filter press 25. The obtained secondary filter residue is the ferric oxide product with a content of 83.88%. The obtained secondary filtrate is the washing water for the leaching residue and is returned to step S5 for dissolution and leaching.

[0103] S7. After further impurity removal and crystallization of the manganese sulfate filtrate obtained in step S5, feed-grade manganese sulfate product is obtained. The main content of the feed-grade manganese sulfate product reaches 99.5%, and the calcium, magnesium, potassium and sodium content of the battery-grade manganese sulfate is less than 50 ppm. All other indicators meet the qualification requirements for battery-grade manganese sulfate.

[0104] The reduction rate of manganese dioxide ore obtained by this process reached 97.83%, the dissolution and leaching rate of manganese sulfate reached 96.55%, the manganese content of the manganese sulfate solution reached 115.21 g / L, the ferric oxide product content reached 83.88%, and the main content of the battery-grade manganese sulfate product reached 99.5%. The calcium, magnesium, potassium, and sodium contents of the battery-grade manganese sulfate were less than 50 ppm, and all other indicators met the qualification requirements for battery-grade manganese sulfate.

[0105] Examples 2-4

[0106] The manganese dioxide ore used in this embodiment is a domestically produced solid manganese dioxide raw material with a manganese content of 49.72%, a moisture content of 31.24%, a manganese dioxide content of 74.09%, and an iron content of 3.37%. The ferrous sulfate heptahydrate used is a ferrous sulfate product produced by Henan Huiyi Hai Environmental Protection Technology Co., Ltd., with a ferrous sulfate heptahydrate content of 99.00%.

[0107] A method for preparing manganese sulfate solution by reducing roasted manganese dioxide ore with ferrous sulfate includes the following steps:

[0108] S1. Manganese dioxide ore is processed to obtain manganese dioxide ore powder, which is stored in manganese dioxide powder silo 7. The mesh size of the manganese dioxide ore powder is not less than 100 mesh, and the proportion between 100 mesh and 150 mesh reaches 97.86%.

[0109] S2. Ferrous sulfate is stored in ferrous sulfate silo 8. Manganese dioxide powder and ferrous sulfate from manganese dioxide powder silo 7 and ferrous sulfate silo 8 are introduced into mixer 11 at a manganese-sulfur ratio of 135:100. The powder is mixed evenly to obtain a mixture of ferrous sulfate and manganese dioxide.

[0110] S3. The mixture of ferrous sulfate and manganese dioxide is introduced into the mixing silo 14, and then fed into the reduction kiln 16 through the mixing silo 14. It is then reduced and roasted at 725℃ for 120 minutes to obtain the roasted manganese sulfate and ferric oxide products. The total manganese content of the roasted manganese sulfate and ferric oxide products is 27.83%, the divalent manganese content is 26.81%, the total iron content is 24.22%, and the reduction rate of manganese dioxide ore reaches 96.33%.

[0111] S4. The calcined products of manganese sulfate and ferric oxide are cooled and ground by a post-processing unit for reducing calcined materials to obtain a mixed powder of manganese sulfate and ferric oxide. The mesh size of the mixed powder of manganese sulfate and ferric oxide is not less than 120 mesh, and the proportion between 120 mesh and 200 mesh reaches 96.50%.

[0112] S5. The mixed powder of manganese sulfate and ferric oxide is introduced into the reduction roasting silo 21, and then introduced into the manganese sulfate dissolution leaching tank 23 through the reduction roasting silo 21. Hot water or washing water of the leaching residue is added at a liquid-to-solid ratio of 2:1 for dissolution and leaching. The leaching temperature is controlled at 85℃, and the dissolution and leaching time is 4 hours. The manganese sulfate dissolution and leaching rate reaches 95.88%. After the dissolution and leaching is completed, the primary filter residue and primary filtrate are separated by a filter press 25. The primary filtrate is a manganese sulfate solution with a manganese concentration of 120.03 g / L. The primary filter residue is ferric oxide filter residue. The iron content of the obtained ferric oxide filter residue reaches 54.17%.

[0113] S6. Add hot water to the ferric oxide filter residue in the filter press at a liquid-to-solid ratio of 2:1 for rinsing. The rinsing temperature is controlled at 70℃ and the rinsing time is 1 hour. After rinsing, separate the secondary filter residue and secondary filtrate through the filter press 25. The obtained secondary filter residue is the ferric oxide product with a content of 80.23%. The obtained secondary filtrate is the washing water for the leaching residue and is returned to step S5 for dissolution and leaching.

[0114] S7. After further impurity removal and crystallization of the manganese sulfate filtrate obtained in step S5, feed-grade manganese sulfate product is obtained. The main content of the feed-grade manganese sulfate product reaches 99.0%, and the calcium, magnesium, potassium and sodium content of the battery-grade manganese sulfate is less than 50 ppm. All other indicators meet the qualification requirements for battery-grade manganese sulfate.

[0115] The reduction rate of manganese dioxide ore obtained by this process reaches 96.33%, the dissolution and leaching rate of manganese sulfate reaches 95.88%, the manganese content of the manganese sulfate solution reaches 120.03 g / L, the ferric oxide product content reaches 80.23%, and the main content of the battery-grade manganese sulfate product reaches 99.00%. The calcium, magnesium, potassium, and sodium content of the battery-grade manganese sulfate is less than 50 ppm, and all other indicators meet the qualification requirements for battery-grade manganese sulfate.

Claims

1. A production device for preparing a manganese sulfate solution by reducing a roasted manganese dioxide ore with ferrous sulfate, characterized in that it comprises include: Manganese dioxide powder silo; Ferrous sulfate silo; The mixer has its feed end connected to the discharge ends of the manganese dioxide powder silo and the ferrous sulfate silo, respectively. A mixing silo, the feed end of which can introduce the mixed material discharged from the mixer; The reduction kiln has its feed end connected to the discharge end of the mixing silo; The feed end of the reduction roasting material post-processing mechanism is connected to the discharge end of the reduction kiln; The reduction roasting silo, with its inlet end and the outlet end of the reduction roasting post-processing mechanism, is used to store the post-processed reduction roasting material. A manganese sulfate dissolution leaching tank is connected to the discharge end of the reduction roasting silo; The filter press has its feed end connected to the manganese sulfate dissolution leaching tank via a leaching conveying pipe, and its cleaning water outlet connected to the manganese sulfate dissolution leaching tank via a rinsing filter liquid pipe, and is also equipped with a filter liquid outlet. A hot water buffer tank is connected to the manganese sulfate dissolution leaching tank and the filter press via a first hot water delivery pipe and a second hot water delivery pipe, respectively. The manganese sulfate leaching filtrate storage tank is connected to the filtrate outlet of the filter press via a manganese sulfate leaching filtrate pipeline.

2. The production apparatus for preparing manganese sulfate solution by reducing roasted manganese dioxide ore with ferrous sulfate according to claim 1, characterized in that: It also includes a manganese dioxide powder pretreatment mechanism, which includes: Crusher; The manganese dioxide pre-conveying unit is located below the discharge end of the crusher; A vertical grinding mill, the feed end of which is connected to the discharge end of the manganese dioxide powder conveying unit; The manganese dioxide downstream conveying unit has its feed end connected to the discharge end of the vertical mill, and its discharge end connected to the feed end of the manganese dioxide powder silo. It is also equipped with a bag dust collector.

3. The production apparatus for preparing manganese sulfate solution by reducing roasted manganese dioxide ore with ferrous sulfate according to claim 2, characterized in that: The manganese dioxide front conveying unit includes a belt conveyor and a manganese dioxide bucket elevator. The belt conveyor is located below the discharge end of the crusher, and the discharge end is connected to the feed end of the manganese dioxide bucket elevator. The discharge end of the manganese dioxide bucket elevator is connected to the vertical grinding mill.

4. The production apparatus for preparing manganese sulfate solution by reducing roasted manganese dioxide ore with ferrous sulfate according to claim 2, characterized in that: The manganese dioxide post-conveying unit includes a manganese dioxide powder conveying pipe and a bag filter dust collector. The inlet end of the manganese dioxide powder conveying pipe is connected to the outlet end of the vertical mill and extends upward to connect to the inlet end of the bag filter dust collector. The ash hopper outlet of the bag filter dust collector is connected to the inlet end of the manganese dioxide powder silo.

5. The production apparatus for preparing manganese sulfate solution by reducing roasted manganese dioxide ore with ferrous sulfate according to claim 1, characterized in that: The post-processing mechanism for the reduced roasted material includes: The slag cooler has its feed end connected to the discharge end of the reduction kiln; A ball mill, the feed end of which is connected to the discharge end of the slag cooler; A vibrating screen is installed below the discharge end of the ball mill, and the discharge end is connected to the feed end of the reduction roasting powder bucket elevator and the reduction roasting silo.

6. The production apparatus for preparing manganese sulfate solution by reducing roasted manganese dioxide ore with ferrous sulfate according to claim 1, characterized in that: The manganese sulfate dissolution and leaching tank is equipped with a stirring device.

7. The production apparatus for preparing manganese sulfate solution by reducing roasted manganese dioxide ore with ferrous sulfate according to claim 1, characterized in that: The manganese dioxide powder silo and the ferrous sulfate silo are located above the mixer; And / or, a mixing screw feeder and a mixing bucket elevator are provided between the mixer and the mixing silo, the feed end of the mixing screw feeder is located below the mixer, the discharge end of the mixing screw feeder is located above the feed end of the mixing bucket elevator, and the discharge end of the mixing bucket elevator extends upward to the top of the mixing silo. And / or, the mixing silo is located on one side of the ferrous sulfate silo, and a reduction kiln and a reduction roasting post-processing mechanism are arranged in sequence below it; And / or, the reduction roasting silo is located above the manganese sulfate dissolution leaching tank.

8. A method for preparing manganese sulfate solution using the production apparatus according to any one of claims 1-7, characterized in that... Includes the following steps: S1. Manganese dioxide ore is processed to obtain manganese dioxide ore powder, which is stored in the manganese dioxide powder silo. The mesh size of the manganese dioxide ore powder is not less than 100 mesh, and the proportion between 100 mesh and 150 mesh reaches more than 95%. S2. Ferrous sulfate is stored in the ferrous sulfate silo. The manganese dioxide powder and ferrous sulfate in the manganese dioxide powder silo and the ferrous sulfate silo are introduced into the mixer at a manganese-sulfur ratio of 120-150:

100. The powder is mixed evenly to obtain a mixture of ferrous sulfate and manganese dioxide. S3. The mixture of ferrous sulfate and manganese dioxide is introduced into the mixing silo and then into the reduction kiln. The mixture is reduced and roasted at 650-780℃ for 100-150 minutes to obtain the roasted manganese sulfate and ferric oxide products. S4. The calcined products of manganese sulfate and ferric oxide are cooled and ground by the post-processing mechanism of the reduced calcined material to obtain a mixed powder of manganese sulfate and ferric oxide. The mixed powder of manganese sulfate and ferric oxide has a mesh size of not less than 120 mesh, and the proportion of 120 mesh to 200 mesh is more than 95.00%. S5. The mixed powder of manganese sulfate and ferric oxide is introduced into the reduction roasting silo, and then introduced into the manganese sulfate dissolution leaching tank through the reduction roasting silo. Hot water or washing water of the leaching residue is added at a liquid-solid ratio of 1.9-3:1 for dissolution and leaching. The leaching temperature is controlled at 80-90℃ and the time is 3-4 hours. After dissolution and leaching are completed, the primary filter residue and primary filtrate are separated by a filter press. The primary filtrate is manganese sulfate solution and the primary filter residue is ferric oxide filter residue.

9. The method for preparing manganese sulfate solution according to claim 8, characterized in that: The process also includes step S6: adding ferric oxide filter residue to hot water at a liquid-to-solid ratio of 1.9-3:1 and rinsing it in a filter press. The rinsing temperature is controlled at 60-80℃ and the rinsing time is 0.8-2 hours. After rinsing, the secondary filter residue and secondary filtrate are separated by a filter press. The secondary filter residue is ferric oxide product, and the secondary filtrate is the washing water for the leaching residue. The filtrate is returned to step S5 for dissolution and leaching.

10. The method for preparing manganese sulfate solution according to claim 8, characterized in that: The manganese dioxide ore powder A1 and ferrous sulfate are mixed at a manganese-sulfur ratio of 135:100.

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