Method for preparing high-quality manganese monoxide by taking medium-low-grade pyrolusite as raw material

Abstract

The invention discloses a method for preparing high-quality manganese monoxide by taking medium-low-grade pyrolusite as a raw material, and relates to the technical field of preparation of high-quality manganese monoxide products. The method comprises the following steps: crushing to prepare powder, blending coal, uniformly mixing, carrying out high-temperature reduction roasting through a reduction kiln to obtain manganese monoxide powder, cooling through a slag cooler, and carrying out magnetic separation in a magnetic separator to obtain concentrate which is a high-quality manganese monoxide product. By means of the magnetic separation process, the concentrate recovery rate reaches 50% or above, the resource utilization rate is remarkably increased, meanwhile, the battery-grade manganese sulfate product is prepared from the tailings through the leaching process, recycling of the tailings is achieved, and economic benefits are further increased; by optimizing the technological process, waste generation is reduced, the influence on the environment is reduced, the manganese content of the obtained manganese monoxide product reaches 60% or above, the quality requirement of high-quality manganese monoxide is met, and the manganese monoxide can be used for battery materials and can replace feed-grade manganese sulfate to be applied to multiple fields of animals and plants, catalysts, electronic materials and the like.

Description

Technical Field

[0001] The invention relates to the technical field of high-quality manganese monoxide product preparation, and in particular to a method for preparing high-quality manganese monoxide by using medium- and low-grade pyrolusite as raw materials. Background Art

[0002] At present, high-quality manganese monoxide has important applications in many fields due to its high purity and excellent physical and chemical properties. The following are its main uses: 1. Battery materials: High-quality manganese monoxide can be used as positive and negative electrode materials for batteries. In alkaline manganese batteries (such as alkaline manganese lithium batteries), the positive electrode material is usually manganese monoxide as the main component, and in lithium-ion batteries (manganese monoxide / graphene composite negative electrode materials), the negative electrode material is usually manganese monoxide as the main component; 2. Replacement of feed-grade manganese sulfate for animals and plants: Manganese is one of the nine essential micronutrients (trace minerals) for healthy animals. It is an essential component of many enzyme systems, including carbohydrate, protein and lipid metabolism. Because animals store very little manganese in their bodies, their diets must contain enough manganese to meet daily needs. Manganese helps animals synthesize fatty acids and cholesterol. It is also necessary for bone strength and reproductive health. Animals need it to effectively utilize biotin, vitamin B1 and vitamin C. Deficiency symptoms include abnormal bone growth / osteoporosis, poor reproductive capacity in ewes and dairy cows, weak offspring, increased fat deposition, abnormal gait in newborn calves and lambs, reduced milk production, poor eggshell formation, and tendon slippage in poultry. Manganese is one of the most essential micronutrients (trace minerals) required for normal plant growth and development. Manganese is essential for the functional systems of plants, including photosynthesis and respiration. Signs of manganese deficiency can be identified by yellowing leaves and stunted plant growth and development. 3. Catalyst: Due to its high catalytic performance, high-quality manganese monoxide can be used as a catalyst. It can catalyze the oxidation reaction of carbon monoxide and hydrocarbons in organic waste gas, thereby purifying waste gas emissions. In addition, it can also be used to catalyze organic synthesis reactions, oxidation reactions and reduction reactions, etc.; 4. Electronic materials: High-quality manganese monoxide can be used to prepare electronic materials such as magnetic materials, ferrite materials and varistors. Its magnetic properties and resistance properties make it have important applications in the field of electronics; 5. Ceramic materials: High-quality manganese monoxide can be used as a colorant for ceramic materials to prepare ceramic products with special colors and textures. It can also improve the hardness, wear resistance and high temperature resistance of ceramic products. In summary, high-quality manganese monoxide has important application value in batteries, replacing feed-grade manganese sulfate in animals and plants, catalysts, electronic materials and ceramic materials. With the continuous advancement of science and technology and the continuous development of industry, the use of high-quality manganese monoxide will continue to expand and deepen.

[0003] At present, the process of industrial production of high-quality manganese monoxide mainly adopts the selection of specific high-quality manganese ore sources for direct reduction to produce high-quality manganese monoxide. However, due to the high quality of this type of ore source, the source is relatively limited and the price of the ore source is relatively high, resulting in the high cost of producing high-quality manganese monoxide and the disadvantage of not being able to produce on a large scale. When medium and low-quality pyrolusite is used for direct reduction to produce manganese monoxide, the total manganese content of the obtained manganese monoxide product is only 35% to 45%, and the quality does not meet the quality requirement of high-quality manganese monoxide with a total manganese content greater than 60.00%, and it cannot be sold as a high-quality manganese monoxide product. Originally, it was intended to use magnetic separation to improve the quality of pyrolusite and then directly reduce and produce high-quality manganese monoxide products, but it was found in the experiment that both manganese and iron in pyrolusite are magnetic, and it is difficult to separate manganese and iron to improve the quality of pyrolusite.

[0004] In view of this, through a large number of research and analysis, it is found that manganese ore contains iron elements, which may be converted into magnetite with strong magnetism during the reduction roasting process, while pyrolusite is non-magnetic or weakly magnetic after being reduced to manganese monoxide through high-temperature roasting. Through a large number of experimental studies, it is found that the manganese monoxide powder produced by the existing medium and low-quality high-iron pyrolusite can be separated from manganese and iron by magnetic separation technology to improve the manganese grade of manganese monoxide, so as to achieve the quality requirement of high-quality manganese monoxide with a total manganese content greater than 60.00%.

[0005] Therefore, a method for preparing high-quality manganese monoxide using medium- and low-grade pyrolusite as raw materials is proposed. Summary of the invention

[0006] The purpose of the present invention is to solve the problems raised in the above background technology. The present invention provides a method for preparing high-quality manganese monoxide using medium and low-grade pyrolusite as raw material.

[0007] In order to achieve the above-mentioned purpose, the present invention specifically adopts the following technical solutions:

[0008] A method for preparing high-quality manganese monoxide using medium- and low-grade pyrolusite as raw materials comprises the steps of crushing and pulverizing, then blending with coal and mixing evenly, and then reducing and roasting in a reduction kiln at high temperature to obtain manganese monoxide powder, and then cooling in a slag cooler and then entering a magnetic separator for magnetic separation. The concentrate obtained after magnetic separation is a high-quality manganese monoxide product.

[0009] Furthermore, the method specifically includes the following steps:

[0010] Step S1: crushing medium and low grade high iron pyrolusite with a crusher, feeding it into a powder making device for grinding, and mixing evenly to obtain high iron pyrolusite powder A1;

[0011] Step S2: Evenly mix the iron-manganese ore powder A1 obtained in step S1 and the coal powder to obtain raw material powder A2;

[0012] Step S3: transporting the raw material powder A2 into a reduction kiln for reduction roasting to obtain clinker powder A3;

[0013] Step S4: the clinker powder A3 is put into a slag cooler for cooling to obtain medium-low quality manganese monoxide powder A4;

[0014] Step S5: transporting the medium and low quality manganese monoxide powder A4 to a dry magnetic separator for magnetic separation to obtain manganese monoxide powder concentrate A5 and manganese monoxide powder tailings A6;

[0015] Step S6: Packing the manganese monoxide powder concentrate A5 by a packaging machine to obtain a high-quality manganese monoxide product A7;

[0016] Step S7: The manganese monoxide powder tailings A6 obtained in step S5 are transported to the leaching process for leaching into a manganese sulfate solution, and are subjected to impurity removal and recrystallization to prepare a battery-grade manganese sulfate product.

[0017] Furthermore, the mesh size of the iron-manganese ore powder A1 prepared in step S1 is greater than 100 meshes, and the proportion of 100 meshes-150 meshes is greater than 95%.

[0018] Furthermore, in step S2, the iron-manganese ore powder A1 and the coal powder are mixed evenly in a mass ratio of 100:15.

[0019] Furthermore, in step S3, the calcination temperature of the reduction kiln is 800-850° C., and the calcination time is 60 minutes.

[0020] Furthermore, in step S4, the temperature of the clinker powder A3 after being cooled in the slag cooler is between 60 and 65°C.

[0021] Furthermore, the magnetic field strength of the dry magnetic separator during magnetic separation in step S5 is 4000 Gs.

[0022] A high-quality manganese monoxide product is prepared by a method for preparing high-quality manganese monoxide using medium- and low-grade pyrolusite as raw materials.

[0023] The beneficial effects of the present invention are as follows:

[0024] The present invention does not rely on a specific high-quality manganese ore source, but utilizes medium- and low-grade high-iron pyrolusite, which is relatively easy to obtain and has a low cost, thereby broadening the source of raw materials. Through the steps of crushing and pulverizing, coal blending, high-temperature reduction roasting, cooling, magnetic separation, etc., the conversion from low-grade ore to high-quality manganese monoxide is achieved. The entire process is simple and easy to operate and control.

[0025] By using medium and low-grade pyrolusite as raw materials, the cost is low, and the process flow is simplified, which reduces energy consumption and raw material consumption in the production process, thereby reducing the overall production cost. Compared with the traditional method, the production process of the present invention is more compact, reduces intermediate links, and improves production efficiency;

[0026] Through the magnetic separation process, the concentrate recovery rate reaches more than 50%, which significantly improves the utilization rate of resources. At the same time, the tailings are used to prepare battery-grade manganese sulfate products through the leaching process, realizing the reuse of tailings and further increasing economic benefits.

[0027] By optimizing the process flow, the generation of waste is reduced and the impact on the environment is lowered. The manganese content of the obtained manganese monoxide product reaches more than 60%, which meets the quality requirements of high-quality manganese monoxide. It can be used in battery materials, replace feed-grade manganese sulfate in animals and plants, catalysts, electronic materials and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The present invention is a flow chart for preparing high-quality manganese monoxide using medium- and low-grade pyrolusite as raw materials. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Generally, the components of the embodiments of the present invention described and shown in the drawings here can be arranged and designed in various different configurations.

[0030] Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] It should be noted that similar reference numerals and letters represent similar items in the following drawings, so once an item is defined in one drawing, it does not need to be further defined and explained in the subsequent drawings. In addition, the terms "first", "second", etc. are only used to distinguish the description and cannot be understood as indicating or implying relative importance.

[0032] In the description of the embodiments of the present invention, it should be noted that the terms "inside", "outside", "upper", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, or are the orientations or positional relationships in which the inventive product is usually placed when used. They are only for the convenience of describing 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.

[0033] like Figure 1 A method for preparing high-quality manganese monoxide using medium- and low-grade pyrolusite as raw materials comprises the steps of crushing and pulverizing, then blending with coal and mixing evenly, and then reducing and roasting in a reduction kiln at high temperature to obtain manganese monoxide powder, and then cooling in a slag cooler and then entering a magnetic separator for magnetic separation. The concentrate obtained after magnetic separation is a high-quality manganese monoxide product.

[0034] The specific steps include:

[0035] Step S1: After crushing the medium and low-grade high-iron pyrolusite with a crusher, the crusher is fed into a powder making device for grinding, and the mixture is evenly mixed to obtain high-iron pyrolusite powder A1, wherein the prepared iron-manganese ore powder A1 has a mesh size greater than 100 meshes, and the proportion of 100-150 meshes reaches more than 95%;

[0036] Step S2: uniformly mixing the iron-manganese ore powder A1 obtained in step S1 and coal powder, wherein the mass ratio of the iron-manganese ore powder A1 to the coal powder is 100:15, to obtain raw meal powder A2;

[0037] Step S3: conveying the raw material powder A2 into a reduction kiln, wherein the roasting temperature of the reduction kiln is 800-850° C. and the roasting time is 60 min, to obtain clinker powder A3;

[0038] Step S4: the clinker powder A3 is put into a slag cooler for cooling. The temperature of the clinker powder A3 after cooling in the slag cooler is 60-65° C., and a medium-low quality manganese monoxide powder A4 is obtained.

[0039] Step S5: conveying the medium and low quality manganese monoxide powder A4 to a dry magnetic separator for magnetic separation, wherein the magnetic field strength of the dry magnetic separator during magnetic separation is 4000 Gs, to obtain manganese monoxide powder concentrate A5 and manganese monoxide powder tailings A6;

[0040] Step S6: Packing the manganese monoxide powder concentrate A5 by a packaging machine to obtain a high-quality manganese monoxide product A7;

[0041] Step S7: The manganese monoxide powder tailings A6 obtained in step S5 are transported to the leaching process for leaching into a manganese sulfate solution, and are subjected to impurity removal and recrystallization to prepare a battery-grade manganese sulfate product.

[0042] Embodiment 1:

[0043] The medium-low quality high-iron pyrolusite used in this example comes from Gabon high-iron pyrolusite, with a manganese content of 40.00%, a manganese dioxide content of 63.27%, and an iron content of 16.70%;

[0044] A method for preparing high-quality manganese monoxide products using medium- and low-quality high-iron pyrolusite as raw materials comprises the following steps:

[0045] S1: After crushing the medium and low grade high iron pyrolusite with a crusher, the crusher is sent to a powder making device for grinding and mixing to obtain high iron pyrolusite powder, wherein the iron manganese ore powder has a mesh size greater than 100 meshes, and the proportion of 100 meshes to 150 meshes reaches 95.88%;

[0046] S2: uniformly mixing the iron-manganese ore powder obtained in the previous step with coal powder in a mass ratio of 100:15 to obtain raw meal powder;

[0047] S3: conveying the raw material powder obtained in the above step into a reduction kiln, and reducing and roasting the raw material powder at 820° C. The reduction and roasting time of the raw material powder in the reduction kiln is 60 minutes to obtain clinker powder;

[0048] S4: The clinker powder obtained in the above step is put into a slag cooler for cooling. After being cooled to 60° C. by the slag cooler, a medium-low quality manganese monoxide powder is obtained. The obtained medium-low quality manganese monoxide powder has a manganese content of 43.00%, a manganese monoxide content of 55.57%, a manganese dioxide content of 0%, and an iron content of 20.30%;

[0049] S5: conveying the medium and low quality manganese monoxide powder obtained in the above step to a dry magnetic separator for magnetic separation, wherein the magnetic field strength of the magnetic separator is 4000 Gs, and obtaining manganese monoxide powder concentrate and manganese monoxide powder tailings by magnetic separation in the dry magnetic separator; wherein the recovery rate of the obtained manganese monoxide powder concentrate is 51.2%, and the recovery rate of the obtained manganese monoxide powder tailings is 48.8%;

[0050] S6: The manganese monoxide powder concentrate obtained in step S5 is packaged by a packaging machine to obtain a high-quality manganese monoxide product, wherein the manganese content of the obtained manganese monoxide product is 60.11% and the iron content is 3.4%;

[0051] The manganese content of the manganese monoxide powder obtained by the process reaches 60.11%, meeting the quality requirement of high-quality manganese monoxide that the total manganese content is greater than 60.00%.

[0052] Embodiment 2:

[0053] The medium-low quality high-iron pyrolusite used in this example comes from South African high-iron pyrolusite, with a manganese content of 37.53%, a manganese dioxide content of 59.36%, and an iron content of 17.77%;

[0054] A method for preparing high-quality manganese monoxide products using medium- and low-quality high-iron pyrolusite as raw materials comprises the following steps:

[0055] S1: After crushing the medium and low grade high iron pyrolusite with a crusher, the crusher is sent to a powder making device for grinding and mixing to obtain high iron pyrolusite powder, wherein the iron manganese ore powder has a mesh size greater than 100 meshes, and the proportion of 100 meshes to 150 meshes reaches 96.78%;

[0056] S2: uniformly mixing the iron-manganese ore powder obtained in the previous step with coal powder in a mass ratio of 100:15 to obtain raw meal powder;

[0057] S3: conveying the raw material powder obtained in the above step into a reduction kiln, and reducing and roasting the raw material powder at 830° C. The reduction and roasting time of the raw material powder in the reduction kiln is 60 minutes to obtain clinker powder;

[0058] S4: The clinker powder obtained in the above step is put into a slag cooler for cooling. After being cooled to 63° C. by the slag cooler, a medium-low quality manganese monoxide powder is obtained. The obtained medium-low quality manganese monoxide powder has a manganese content of 41.80%, a manganese monoxide content of 53.96%, a manganese dioxide content of 0%, and an iron content of 21.70%;

[0059] S5: conveying the medium and low quality manganese monoxide powder obtained in the above step to a dry magnetic separator for magnetic separation, wherein the magnetic field strength of the magnetic separator is 4000 Gs, and obtaining manganese monoxide powder concentrate and manganese monoxide powder tailings by magnetic separation in the dry magnetic separator; wherein the recovery rate of the obtained manganese monoxide powder concentrate is 50.22%, and the recovery rate of the obtained manganese monoxide powder tailings is 49.78%;

[0060] S6: The manganese monoxide powder concentrate obtained in step S5 is packaged by a packaging machine to obtain a high-quality manganese monoxide product, wherein the manganese content of the obtained manganese monoxide product is 60.01% and the iron content is 5.1%;

[0061] The manganese content of the manganese monoxide powder obtained by the process reaches 60.01%, meeting the quality requirement of high-quality manganese monoxide that the total manganese content is greater than 60.00%.

[0062] Embodiment 3:

[0063] The medium-low quality high-iron pyrolusite used in this example comes from Australian high-iron pyrolusite, with a manganese content of 43.62%, a manganese dioxide content of 68.99%, and an iron content of 14.58%;

[0064] A method for preparing high-quality manganese monoxide products using medium- and low-quality high-iron pyrolusite as raw materials comprises the following steps:

[0065] S1: After crushing the medium and low grade high iron pyrolusite with a crusher, the crusher is sent to a powder making device for grinding and mixing to obtain high iron pyrolusite powder, wherein the iron manganese ore powder has a mesh size greater than 100 meshes, and the proportion of 100 meshes to 150 meshes reaches 96.33%;

[0066] S2: uniformly mixing the iron-manganese ore powder obtained in the previous step with coal powder in a mass ratio of 100:15 to obtain raw meal powder;

[0067] S3: conveying the raw material powder obtained in the above step into a reduction kiln, and reducing and roasting the raw material powder at 820° C. The reduction and roasting time of the raw material powder in the reduction kiln is 60 minutes to obtain clinker powder;

[0068] S4: The clinker powder obtained in the above step is put into a slag cooler for cooling. After being cooled to 63° C. by the slag cooler, a medium-low quality manganese monoxide powder is obtained. The obtained medium-low quality manganese monoxide powder has a manganese content of 47.36%, a manganese monoxide content of 61.13%, a manganese dioxide content of 0%, and an iron content of 16.88%;

[0069] S5: conveying the medium and low quality manganese monoxide powder obtained in the above step to a dry magnetic separator for magnetic separation, wherein the magnetic field strength of the magnetic separator is 4000 Gs, and obtaining manganese monoxide powder concentrate and manganese monoxide powder tailings by magnetic separation in the dry magnetic separator; wherein the recovery rate of the obtained manganese monoxide powder concentrate is 55.78%, and the recovery rate of the obtained manganese monoxide powder tailings is 44.22%;

[0070] S6: The manganese monoxide powder concentrate obtained in step S5 is packaged by a packaging machine to obtain a high-quality manganese monoxide product, wherein the manganese content of the obtained manganese monoxide product is 62.13% and the iron content is 2.9%;

[0071] The manganese content of the manganese monoxide powder obtained by the process reaches 62.13%, meeting the quality requirement of high-quality manganese monoxide that the total manganese content is greater than 60.00%.

[0072] In summary, the present invention provides a method for preparing a high-grade manganese monoxide product using medium- and low-grade high-iron pyrolusite as raw materials, so that industrial production of high-quality manganese monoxide can be carried out on a large scale and applied. The present invention has the advantages of wide raw material sources, simple process, low production cost, short production process, high product profit, etc., and the concentrate recovery rate after magnetic separation reaches more than 50%, and the tailings can continue to be leached to prepare battery-grade manganese sulfate products, thereby achieving the purpose of maximizing resource utilization and profit utilization of medium- and low-grade high-iron pyrolusite.

[0073] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions only describe the principles of the present invention. The present invention may be subject to various changes and improvements without departing from the spirit and scope of the present invention. These changes and improvements fall within the scope of the present invention. The scope of protection claimed by the present invention is defined by the attached claims and their equivalents.

Claims

1. A method for preparing high-quality manganese monoxide using medium- and low-grade pyrolusite as raw material, characterized in that: The process includes crushing and pulverizing, then evenly mixing with coal, and then reducing and roasting in a reduction kiln at high temperature to obtain manganese monoxide powder. The powder is then cooled in a slag cooler and then sent to a magnetic separator for magnetic separation. The concentrate obtained after magnetic separation is a high-quality manganese monoxide product.

2. The method for preparing high-quality manganese monoxide using medium- and low-grade pyrolusite as raw material according to claim 1, characterized in that: The specific steps include: Step S1: crushing medium and low grade high iron pyrolusite with a crusher, feeding it into a powder making device for grinding, and mixing evenly to obtain high iron pyrolusite powder A1; Step S2: Evenly mix the iron-manganese ore powder A1 obtained in step S1 and the coal powder to obtain raw material powder A2; Step S3: transporting the raw material powder A2 into a reduction kiln for reduction roasting to obtain clinker powder A3; Step S4: the clinker powder A3 is put into a slag cooler for cooling to obtain medium-low quality manganese monoxide powder A4; Step S5: transporting the medium and low quality manganese monoxide powder A4 to a dry magnetic separator for magnetic separation to obtain manganese monoxide powder concentrate A5 and manganese monoxide powder tailings A6; Step S6: Packing the manganese monoxide powder concentrate A5 by a packaging machine to obtain a high-quality manganese monoxide product A7; Step S7: The manganese monoxide powder tailings A6 obtained in step S5 are transported to the leaching process for leaching into a manganese sulfate solution, and are subjected to impurity removal and recrystallization to prepare a battery-grade manganese sulfate product.

3. The method for preparing high-quality manganese monoxide using medium- and low-grade pyrolusite as raw material according to claim 2, characterized in that: The mesh size of the iron-manganese ore powder A1 prepared in step S1 is greater than 100 meshes, and the proportion of 100 meshes-150 meshes is more than 95%.

4. The method for preparing high-quality manganese monoxide using medium- and low-grade pyrolusite as raw material according to claim 2, characterized in that: In step S2, the iron-manganese ore powder A1 and the coal powder are mixed evenly in a mass ratio of 100:

15.

5. The method for preparing high-quality manganese monoxide using medium- and low-grade pyrolusite as raw material according to claim 2, characterized in that: In step S3, the calcination temperature of the reduction kiln is 800-850° C., and the calcination time is 60 minutes.

6. The method for preparing high-quality manganese monoxide using medium- and low-grade pyrolusite as raw material according to claim 2, characterized in that: In step S4, the temperature of the clinker powder A3 after being cooled in the slag cooler is 60-65°C.

7. The method for preparing high-quality manganese monoxide using medium- and low-grade pyrolusite as raw material according to claim 2, characterized in that: In step S5, the magnetic field strength of the dry magnetic separator during magnetic separation is 4000 Gs.

8. A high-quality manganese monoxide product prepared by the method for preparing high-quality manganese monoxide using medium- and low-grade pyrolusite as raw material as claimed in any one of claims 1 to 7.

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