Method for preparing unburned refractory brick by using manganese dioxide waste residue
By treating electrolytic manganese dioxide waste residue with materials such as magnesium silicide and expanded graphite under a nitrogen atmosphere to generate graphene, non-fired refractory bricks can be prepared. This solves the problems of resource utilization of manganese dioxide waste residue and insufficient strength of refractory bricks, and realizes the preparation of high-strength refractory bricks suitable for high-temperature industries.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- QIDONG FENGSHUN MANGANESE IND CO LTD
- Filing Date
- 2026-03-26
- Publication Date
- 2026-07-10
AI Technical Summary
The resource utilization rate of manganese dioxide waste residue is low, and the raw material cost of traditional unburned refractory bricks is high and the compressive strength and high-temperature flexural strength are insufficient, making it difficult to meet the needs of high-end high-temperature kilns.
Electrolytic manganese dioxide waste powder is ultrasonically treated with magnesium silicide, expanded graphite, polyvinylpyrrolidone, and boron nitride under a nitrogen atmosphere to generate graphene. This graphene is then mixed with andalusite powder, silica powder, and corundum powder, and combined with binders such as phenolic resin to prepare unburned refractory bricks. The high-strength skeleton support of graphene and the lubrication of boron nitride work synergistically to improve the compressive strength and high-temperature flexural strength of the refractory bricks.
It realizes the resource utilization of electrolytic manganese dioxide waste residue, significantly improves the compressive strength and high-temperature flexural strength of unburned refractory bricks, reduces production costs, and is suitable for high-temperature industrial fields.
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Figure CN122355718A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of refractory brick technology, specifically to a method for preparing unburned refractory bricks using manganese dioxide waste residue. Background Technology
[0002] Currently, the disposal method for manganese dioxide waste is mainly stockpiling, resulting in extremely low resource utilization rate. How to achieve its high-value utilization has become a technical problem that urgently needs to be solved in the industry.
[0003] Unfired refractory bricks are widely used in high-temperature industries such as metallurgy, building materials, and chemicals due to their advantages, including no need for high-temperature sintering, low energy consumption, and short production cycles. Traditional unfired refractory bricks are primarily made from high-quality raw materials such as mullite and silicon carbide, resulting in high raw material costs. Furthermore, existing unfired refractory bricks still have shortcomings in terms of compressive strength and high-temperature flexural strength, making it difficult to meet the requirements of high-end high-temperature kilns. Summary of the Invention
[0004] The purpose of this invention is to overcome the shortcomings of the existing technology and provide a method for preparing unburned refractory bricks using manganese dioxide waste residue. The unburned refractory bricks prepared by this application have excellent compressive strength and high-temperature flexural strength.
[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A method for preparing non-fired refractory bricks using manganese dioxide waste residue includes the following steps: (1) Wash the electrolytic manganese dioxide waste residue with water, dry it, and crush it to obtain electrolytic manganese dioxide waste residue powder; (2) Add electrolytic manganese dioxide waste powder, magnesium silicide, expanded graphite, polyvinylpyrrolidone, and boron nitride to a solvent, disperse evenly, sonicate, centrifuge, filter, and heat treat under a nitrogen atmosphere to obtain the precursor. (3) Mix the precursor, andalusite powder, silica powder and corundum powder evenly, then mix them evenly with binder and additives, press them into shape, and heat treat them to obtain unburned refractory bricks.
[0006] This application pre-treats electrolytic manganese dioxide waste residue to obtain electrolytic manganese dioxide waste residue powder. The electrolytic manganese dioxide waste residue powder is then ultrasonically reacted with magnesium silicide, expanded graphite, polyvinylpyrrolidone, and boron nitride, followed by heat treatment under a nitrogen atmosphere. The magnesium silicide is then converted into... Graphene is generated in situ from expanded graphite via liquid-phase exfoliation. Providing a high-strength framework support, the in-situ generated graphene possesses an ultra-high specific surface area and excellent mechanical properties, and can be used as a filler. The porosity between the boron nitride and the electrolytic manganese dioxide residue effectively improves the compactness. The boron nitride acts as a lubricating phase and an auxiliary reinforcing phase. The synergistic effect of manganese slag powder and graphene effectively improves the compressive strength and high-temperature flexural strength of unburned refractory bricks. Finally, the precursor is combined with andalusite powder, silica powder, corundum powder, binder, and additives. The phase transformation expansion of andalusite powder offsets the shrinkage, and the silica powder increases the density and strength. Under the synergistic effect of multiple components, the compressive strength and high-temperature flexural strength of unburned refractory bricks are further improved.
[0007] The method of this application simultaneously realizes the resource utilization of electrolytic manganese dioxide waste residue, solves the technical problems of high raw material cost and difficult disposal of industrial waste residue in traditional refractory bricks, and has broad application prospects and economic value.
[0008] In some embodiments, the mass ratio of the electrolytic manganese dioxide waste powder, magnesium silicide, expanded graphite, polyvinylpyrrolidone, boron nitride, and solvent is 100:(25~30):(15~18):(15~18):(2~5):(400~1000).
[0009] In some embodiments, the solvent is at least one of acetone, ethanol, and N-methylpyrrolidone.
[0010] In some embodiments, the power of the ultrasonic treatment is 200-500W; the duration of the ultrasonic treatment is 30-50 minutes.
[0011] In some embodiments, the nitrogen flow rate is 35-40 L / h.
[0012] In some embodiments, the heat treatment in step (2) is performed at a temperature of 1380~1420°C for 1~4 hours.
[0013] In some embodiments, the mass ratio of the precursor, andalusite powder, silica powder and corundum powder is (40~45):(20~25):(20~25):(10~15).
[0014] In some embodiments, the mass ratio of the precursor, binder, and auxiliaries is (40~45):(2~3):(1~2).
[0015] In some embodiments, the binder is prepared by mixing phenolic resin, isopropyl tris(dodecylbenzenesulfonic acid) titanate, and polysilazane at a mass ratio of 1:(0.1~0.2):(0.8~1.2) at 60~80°C to obtain the binder.
[0016] This application uses phenolic resin, isopropyl tris(dodecylbenzenesulfonic acid) titanate, and polysilazane as binders, which can form various chemical bonds with the raw materials (such as hydrogen bonds), effectively improving the bonding effect, preventing the raw materials from agglomerating, improving interfacial compatibility, and further improving the compressive strength and high-temperature flexural strength of unburned refractory bricks.
[0017] In some embodiments, the pressing pressure is 180~250MPa and the time is 6~12min.
[0018] In some embodiments, the heat treatment in step (3) is performed at a temperature of 260~300°C for 18~36 hours.
[0019] In some embodiments, the additive is borax.
[0020] The beneficial effects of this invention are as follows: This application obtains electrolytic manganese dioxide waste powder through pretreatment of electrolytic manganese dioxide waste residue. The electrolytic manganese dioxide waste powder is then ultrasonically treated with magnesium silicide, expanded graphite, polyvinylpyrrolidone, and boron nitride, followed by heat treatment under a nitrogen atmosphere. The magnesium silicide is then converted into… Graphene is generated in situ from expanded graphite via liquid-phase exfoliation. Providing a high-strength framework support, the in-situ generated graphene possesses an ultra-high specific surface area and excellent mechanical properties, and can be used as a filler. The porosity between the boron nitride and the electrolytic manganese dioxide residue effectively improves the compactness. The boron nitride acts as a lubricating phase and an auxiliary reinforcing phase. The synergistic effect of manganese slag powder and graphene effectively improves the compressive strength and high-temperature flexural strength of unburned refractory bricks. Finally, the precursor is combined with andalusite powder, silica powder, corundum powder, binder, and additives. The phase transformation expansion of andalusite powder offsets the shrinkage, and the silica powder increases the density and strength. Under the synergistic effect of multiple components, the compressive strength and high-temperature flexural strength of unburned refractory bricks are further improved. Attached Figure Description
[0021] Figure 1 This is a SEM image of the electrolytic manganese dioxide waste powder from Example 1.
[0022] Figure 2 This is a SEM image of the precursor of Example 1. Detailed Implementation
[0023] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.
[0024] In this application, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.
[0025] The raw materials used in the examples and comparative examples are as follows: The electrolytic manganese dioxide residue was sourced from Hunan Shunlong New Energy. The elemental composition, determined by X-ray fluorescence analysis, is shown in Table 1.
[0026] Table 1 Magnesium silicide: 1250 mesh, commercially available.
[0027] Phenolic resin: Weilin Materials, brand name WL-7705.
[0028] Expanded graphite: Shandong Shuangyu Carbon, grade EG350.
[0029] Polyvinylpyrrolidone: Polyvinylpyrrolidone K30, commercially available.
[0030] Boron nitride: 1250 mesh, commercially available.
[0031] Isopropyl tris(dodecylbenzenesulfonic acid) titanate, commercially available.
[0032] Polysilazane: IOTA silicone oil, grade IOTA 9150.
[0033] andalusite powder: 325 mesh, commercially available.
[0034] Silica powder: 1250 mesh, commercially available.
[0035] Corundum powder: White corundum, 600 mesh, commercially available.
[0036] Unless otherwise specified, all components, raw materials, or instruments used in the embodiments and comparative examples of this invention are commercially available, and the same type of components and raw materials are used in each parallel experiment. Example 1
[0037] A method for preparing non-fired refractory bricks using manganese dioxide waste residue includes the following steps: (1) The electrolytic manganese dioxide waste residue was washed twice with water at 50°C, dried in a drying oven at 105°C until constant weight, and then pulverized to 2000 mesh to obtain electrolytic manganese dioxide waste residue powder. The SEM image of the electrolytic manganese dioxide waste residue powder is shown below. Figure 1 As shown; (2) Electrolytic manganese dioxide waste powder, magnesium silicide, expanded graphite, polyvinylpyrrolidone, and boron nitride were added to N-methylpyrrolidone and dispersed at 200 rpm for 60 min at 50 °C. Then, the mixture was ultrasonically treated with 400 W for 40 min, centrifuged, filtered, and placed in a nitriding furnace. Nitrogen gas was introduced at a flow rate of 35 L / h, and the temperature was increased to 1400 °C at a heating rate of 5 °C / min. The temperature was then maintained at 1400 °C for 2 h to obtain the precursor. The SEM image of the precursor is shown below. Figure 2 As shown; The mass ratio of the electrolytic manganese dioxide waste powder, magnesium silicide, expanded graphite, polyvinylpyrrolidone, boron nitride, and N-methylpyrrolidone is 100:25:18:18:5:600.
[0038] (3) Phenolic resin, isopropyl tris(dodecylbenzenesulfonic acid) titanate and polysilazane are mixed at 65°C and 100 rpm for 30 min in a mass ratio of 1:0.1:1.2 to obtain a binder.
[0039] The precursor, andalusite powder, silica powder, and corundum powder were added to the mixer in a mass ratio of 40:25:20:15 and mixed at 800 rpm for 15 minutes. Then, the mixture was mixed with binder and borax at 800 rpm for 8 minutes. The mixture was then pressed in a friction brick press at a pressure of 220 MPa for 10 minutes. Finally, the bricks were dried in a drying kiln at 280℃ for 24 hours to obtain unfired refractory bricks.
[0040] The mass ratio of the precursor, binder, and borax is 40:3:1. Example 2
[0041] The difference between Example 2 and Example 1 is that the mass ratios of electrolytic manganese dioxide waste powder, magnesium silicide, expanded graphite, polyvinylpyrrolidone, boron nitride, and N-methylpyrrolidone are different, while all other components are the same.
[0042] In this embodiment, the mass ratio of electrolytic manganese dioxide waste powder, magnesium silicide, expanded graphite, polyvinylpyrrolidone, boron nitride, and N-methylpyrrolidone is 100:30:15:15:2:600. Example 3
[0043] The difference between Example 3 and Example 1 is that the mass ratio of phenolic resin, isopropyl tris(dodecylbenzenesulfonic acid) titanate, and polysilazane is different, while all other components are the same.
[0044] In this embodiment, the mass ratio of phenolic resin, isopropyltris(dodecylbenzenesulfonic acid) titanate, and polysilazane is 1:0.2:1.8. Example 4
[0045] The difference between Example 4 and Example 1 is that the mass ratio of the precursor, andalusite powder, silica powder, and corundum powder is different, while everything else is the same.
[0046] In this embodiment, the mass ratio of the precursor, andalusite powder, silica powder, and corundum powder is 45:20:25:10. Example 5
[0047] Example 5 differs from Example 1 in that the mass ratio of the precursor, andalusite powder, silica powder, and corundum powder is different, while everything else is the same.
[0048] In this embodiment, the mass ratio of the precursor, andalusite powder, silica powder, and corundum powder is 30:32.5:32.5:5. Example 6
[0049] The difference between Example 6 and Example 1 is that the mass ratio of the precursor, andalusite powder, silica powder, and corundum powder is different, while everything else is the same.
[0050] In this embodiment, the mass ratio of the precursor, andalusite powder, silica powder, and corundum powder is 60:10:10:20. Example 7
[0051] The difference between Example 7 and Example 1 is that the nitrogen flow rate is 40 L / h, while everything else is the same. Example 8
[0052] The difference between Example 8 and Example 1 is that the nitrogen flow rate is 25 L / h, while everything else is the same. Example 9
[0053] The difference between Example 9 and Example 1 is that the nitrogen flow rate is 50 L / h, while everything else is the same.
[0054] Comparative Example 1 A method for preparing non-fired refractory bricks using manganese dioxide waste residue includes the following steps: (1) Wash the electrolytic manganese dioxide waste residue twice with water at 50°C, dry it in a drying oven at 105°C until constant weight, and pulverize it to 2000 mesh to obtain electrolytic manganese dioxide waste residue powder. (2) Add electrolytic manganese dioxide waste powder, magnesium silicide, expanded graphite, polyvinylpyrrolidone, and boron nitride to N-methylpyrrolidone, disperse at 50°C at 200 rpm for 60 min, then sonicate at 400 W for 40 min, centrifuge, filter, load into nitriding furnace, introduce hydrogen at a flow rate of 35 L / h, heat to 1400°C at a heating rate of 5°C / min, and hold at 1400°C for 2 h to obtain the precursor; The mass ratio of the electrolytic manganese dioxide waste powder, magnesium silicide, expanded graphite, polyvinylpyrrolidone, boron nitride, and N-methylpyrrolidone is 100:25:18:18:5:600.
[0055] (3) Phenolic resin, isopropyl tris(dodecylbenzenesulfonic acid) titanate and polysilazane are mixed at 65°C and 100 rpm for 30 min in a mass ratio of 1:0.1:1.2 to obtain a binder.
[0056] The precursor, andalusite powder, silica powder, and corundum powder were added to the mixer in a mass ratio of 40:25:20:15 and mixed at 800 rpm for 15 minutes. Then, the mixture was mixed with binder and borax at 800 rpm for 8 minutes. The mixture was then pressed in a friction brick press at a pressure of 220 MPa for 10 minutes. Finally, the bricks were dried in a drying kiln at 280℃ for 24 hours to obtain unfired refractory bricks.
[0057] The mass ratio of the precursor, binder, and borax is 40:3:1.
[0058] Comparative Example 2 A method for preparing non-fired refractory bricks using manganese dioxide waste residue includes the following steps: (1) Wash the electrolytic manganese dioxide waste residue twice with water at 50°C, dry it in a drying oven at 105°C until constant weight, and pulverize it to 2000 mesh to obtain electrolytic manganese dioxide waste residue powder. (2) Add electrolytic manganese dioxide waste powder, expanded graphite, polyvinylpyrrolidone, and boron nitride to N-methylpyrrolidone, disperse at 50°C at 200 rpm for 60 min, then sonicate at 400 W for 40 min, centrifuge, filter, load into nitriding furnace, introduce nitrogen at a flow rate of 35 L / h, heat to 1400°C at a heating rate of 5°C / min, and hold at 1400°C for 2 h to obtain the precursor; The mass ratio of the electrolytic manganese dioxide waste powder, expanded graphite, polyvinylpyrrolidone, boron nitride, and N-methylpyrrolidone is 100:18:18:5:600.
[0059] (3) Phenolic resin, isopropyl tris(dodecylbenzenesulfonic acid) titanate and polysilazane are mixed at 65°C and 100 rpm for 30 min in a mass ratio of 1:0.1:1.2 to obtain a binder.
[0060] The precursor, andalusite powder, silica powder, and corundum powder were added to the mixer in a mass ratio of 40:25:20:15 and mixed at 800 rpm for 15 minutes. Then, the mixture was mixed with binder and borax at 800 rpm for 8 minutes. The mixture was then pressed in a friction brick press at a pressure of 220 MPa for 10 minutes. Finally, the bricks were dried in a drying kiln at 280℃ for 24 hours to obtain unfired refractory bricks.
[0061] The mass ratio of the precursor, binder, and borax is 40:3:1.
[0062] Comparative Example 3 A method for preparing non-fired refractory bricks using manganese dioxide waste residue includes the following steps: (1) Wash the electrolytic manganese dioxide waste residue twice with water at 50°C, dry it in a drying oven at 105°C until constant weight, and pulverize it to 2000 mesh to obtain electrolytic manganese dioxide waste residue powder. (2) Add electrolytic manganese dioxide waste powder, magnesium silicide and boron nitride to N-methylpyrrolidone, disperse at 50°C at 200 rpm for 60 min, then sonicate at 400 W for 40 min, centrifuge, filter, load into nitriding furnace, introduce nitrogen at a flow rate of 35 L / h, heat to 1400°C at a heating rate of 5°C / min, and keep at 1400°C for 2 h to obtain the precursor; The mass ratio of the electrolytic manganese dioxide waste powder, magnesium silicide, boron nitride, and N-methylpyrrolidone is 100:25:5:600.
[0063] (3) Phenolic resin, isopropyl tris(dodecylbenzenesulfonic acid) titanate and polysilazane are mixed at 65°C and 100 rpm for 30 min in a mass ratio of 1:0.1:1.2 to obtain a binder.
[0064] The precursor, andalusite powder, silica powder, and corundum powder were added to the mixer in a mass ratio of 40:25:20:15 and mixed at 800 rpm for 15 minutes. Then, the mixture was mixed with binder and borax at 800 rpm for 8 minutes. The mixture was then pressed in a friction brick press at a pressure of 220 MPa for 10 minutes. Finally, the bricks were dried in a drying kiln at 280℃ for 24 hours to obtain unfired refractory bricks.
[0065] The mass ratio of the precursor, binder, and borax is 40:3:1.
[0066] Comparative Example 4 The difference between Comparative Example 4 and Example 1 is that the mass ratios of electrolytic manganese dioxide waste powder, magnesium silicide, expanded graphite, polyvinylpyrrolidone, boron nitride, and N-methylpyrrolidone are different in Comparative Example 4, while all other components are the same.
[0067] In this comparative example, the mass ratio of electrolytic manganese dioxide waste powder, magnesium silicide, expanded graphite, polyvinylpyrrolidone, boron nitride, and N-methylpyrrolidone is 100:15:30:30:1:600.
[0068] Comparative Example 5 The difference between Comparative Example 5 and Example 1 is that the mass ratios of electrolytic manganese dioxide waste powder, magnesium silicide, expanded graphite, polyvinylpyrrolidone, boron nitride, and N-methylpyrrolidone in Comparative Example 5 are different, while all other components are the same.
[0069] In this comparative example, the mass ratio of electrolytic manganese dioxide waste powder, magnesium silicide, expanded graphite, polyvinylpyrrolidone, boron nitride, and N-methylpyrrolidone is 100:40:5:5:8:600.
[0070] Comparative Example 6 The difference between Comparative Example 6 and Example 1 is that the binder in Comparative Example 6 is a single phenolic resin, while everything else is the same.
[0071] A method for preparing non-fired refractory bricks using manganese dioxide waste residue includes the following steps: (1) Wash the electrolytic manganese dioxide waste residue twice with water at 50°C, dry it in a drying oven at 105°C until constant weight, and pulverize it to 2000 mesh to obtain electrolytic manganese dioxide waste residue powder. (2) Add electrolytic manganese dioxide waste powder, magnesium silicide, expanded graphite, polyvinylpyrrolidone, and boron nitride to N-methylpyrrolidone, disperse at 50°C at 200 rpm for 60 min, then sonicate at 400 W for 40 min, centrifuge, filter, load into nitriding furnace, introduce nitrogen at a flow rate of 35 L / h, heat to 1400°C at a heating rate of 5°C / min, and hold at 1400°C for 2 h to obtain the precursor; The mass ratio of the electrolytic manganese dioxide waste powder, magnesium silicide, expanded graphite, polyvinylpyrrolidone, boron nitride, and N-methylpyrrolidone is 100:25:18:18:5:600.
[0072] (3) Add the precursor, andalusite powder, silica powder and corundum powder to the mixer in a mass ratio of 40:25:20:15 and mix at 800 rpm for 15 min. Then mix with phenolic resin and borax at 800 rpm for 8 min. Press the mixture at 220 MPa for 10 min in a friction brick press. Finally, dry the mixture in a drying kiln at 280℃ for 24 h to obtain unfired refractory bricks.
[0073] The mass ratio of the precursor, phenolic resin, and borax is 40:3:1.
[0074] The performance of the embodiments and comparative examples is as follows: Table 2 According to GB / T 2542 standard, the compressive strength test adopts a compression test. A standard-sized brick sample is loaded on a testing machine, the maximum failure load is recorded, and the compressive strength is calculated using a formula. During the test, the load application rate should be 5 ± 0.5 kN / s to ensure that the sample fails under standard conditions. For the high-temperature flexural strength test, according to GB / T34218-2017, the specimen is heated to a set temperature (400°C in this patent), and a flexural strength test is conducted under high-temperature conditions. The maximum flexural load of the sample is recorded through a three-point bending test, the high-temperature flexural strength is calculated, and multiple repeated tests are performed to obtain the average value.
[0075] As can be seen from Table 1, the unburned refractory bricks prepared in this application can effectively improve the compressive strength and high-temperature flexural strength of unburned refractory bricks.
[0076] Comparing Example 1 with Comparative Examples 1-3, it can be seen that in this application, magnesium silicide, expanded graphite, and polyvinylpyrrolidone need to be added simultaneously, which are essential for improving the compressive strength and high-temperature flexural strength of unburned refractory bricks. At the same time, nitrogen needs to be introduced. Thus, with specific raw materials and specific preparation methods in this application, the compressive strength and high-temperature flexural strength of unburned refractory bricks are effectively improved.
[0077] Comparing Example 1 with Comparative Examples 4-5, it can be seen that by controlling the mass ratio of electrolytic manganese dioxide waste powder, magnesium silicide, expanded graphite, polyvinylpyrrolidone, boron nitride, and solvent to 100:(25-30):(15-18):(15-18):(2-5):(400-1000), this application significantly improves the compressive strength and high-temperature flexural strength of unburned refractory bricks.
[0078] Comparing Example 1 and Comparative Example 6, it can be seen that using the specific binder of this application can significantly improve the compressive strength and high-temperature flexural strength of unburned refractory bricks.
[0079] Comparing Examples 1 and 4 with Examples 5 and 6, it can be seen that by controlling the mass ratio of precursor, andalusite powder, silica powder, and corundum powder to (40-45):(20-25):(20-25):(10-15), this application further improves the compressive strength and high-temperature flexural strength of unburned refractory bricks.
[0080] Comparing Examples 1 and 7 with Examples 8 and 9, it can be seen that by controlling the flow rate of nitrogen to 35-40 L / h, this application further improves the compressive strength and high-temperature flexural strength of unburned refractory bricks.
[0081] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.
Claims
1. A method for preparing non-fired refractory bricks using manganese dioxide waste residue, characterized in that, Includes the following steps: (1) Wash the electrolytic manganese dioxide waste residue with water, dry it, and crush it to obtain electrolytic manganese dioxide waste residue powder; (2) Add electrolytic manganese dioxide waste powder, magnesium silicide, expanded graphite, polyvinylpyrrolidone, and boron nitride to a solvent, disperse evenly, sonicate, centrifuge, filter, and heat treat under a nitrogen atmosphere to obtain the precursor. (3) Mix the precursor, andalusite powder, silica powder and corundum powder evenly, then mix them evenly with binder and additives, press them into shape, and heat treat them to obtain unburned refractory bricks.
2. The method for preparing non-fired refractory bricks using manganese dioxide waste slag according to claim 1, characterized in that, The mass ratio of the electrolytic manganese dioxide waste powder, magnesium silicide, expanded graphite, polyvinylpyrrolidone, boron nitride, and solvent is 100:(25~30):(15~18):(15~18):(2~5):(400~1000).
3. The method for preparing non-fired refractory bricks using manganese dioxide waste slag according to claim 1, characterized in that, The power of the ultrasonic treatment is 200~500W; the duration of the ultrasonic treatment is 30~50min.
4. The method for preparing non-fired refractory bricks using manganese dioxide waste slag according to claim 1, characterized in that, The flow rate of the nitrogen gas is 35~40 L / h.
5. The method for preparing non-fired refractory bricks using manganese dioxide waste slag according to claim 1, characterized in that, The heat treatment in step (2) is performed at a temperature of 1380~1420℃ for 1~4 hours.
6. The method for preparing non-fired refractory bricks using manganese dioxide waste slag according to claim 1, characterized in that, The mass ratio of the precursor, andalusite powder, silica powder, and corundum powder is (40~45):(20~25):(20~25):(10~15).
7. The method for preparing non-fired refractory bricks using manganese dioxide waste slag according to claim 1, characterized in that, The mass ratio of the precursor, binder, and auxiliaries is (40~45):(2~3):(1~2).
8. The method for preparing non-fired refractory bricks using manganese dioxide waste slag according to claim 1, characterized in that, The binder is prepared by mixing phenolic resin, isopropyl tris(dodecylbenzenesulfonic acid) titanate, and polysilazane at a mass ratio of 1:(0.1~0.2):(0.8~1.2) at 60~80°C to obtain the binder.
9. The method for preparing non-fired refractory bricks using manganese dioxide waste slag according to claim 1, characterized in that, The pressing pressure is 180~250MPa, and the time is 6~12min.
10. The method for preparing non-fired refractory bricks using manganese dioxide waste slag according to claim 1, characterized in that, The heat treatment in step (3) is performed at a temperature of 260~300℃ for 18~36h.