All-solid-waste metallurgical slag archaized brick and preparation method thereof

Abstract

The invention provides an all-solid-waste metallurgical slag archaized brick and a preparation method thereof.The archaized brick is a substance with diopside, akermanite, calcium ferrite and corundum as phases formed by firing a compression molding substance of a silicon-manganese slag and magnesium slag composite material, and the preparation method comprises the steps that dried silicon-manganese slag and magnesium slag are mixed according to the mass ratio of (0-0.7): (1-0.3); pressing into a green body under the load of 8t, and sufficiently firing the green body at the temperature of 1100-1140 DEG C to obtain the archaized brick. By means of the scheme, the problems that a traditional archaized brick manufacturing process is complex and the investment cost is too high can be effectively solved, the all-solid-waste metallurgical slag archaized brick is prepared from the silicon-manganese slag, the magnesium slag and other solid waste raw materials, environmental pollution is reduced, the production cost is reduced, and finally energy conservation, environmental protection and economic benefits are doubly improved.

Description

Technical Field

[0001] The invention relates to the technical field of solid waste metallurgical slag, and in particular to an all-solid waste metallurgical slag antique brick and a preparation method thereof. Background Art

[0002] Antique tiles are a type of glazed ceramic tiles. The base is made of stoneware (water absorption rate is about 3%) or stoneware (water absorption rate is about 8%). They are used for building walls and floors. Because of their patterns and textures, they are similar to the effect of stone veneers after long-term use. In the industry, they are generally referred to as antique tiles.

[0003] At present, the production of modern antique tiles mainly relies on traditional raw materials such as clay. The source of these raw materials is stable and widely used. However, with the gradual depletion of natural resources and the improvement of environmental protection awareness, the cost of using traditional raw materials to produce antique tiles is constantly rising, facing the problem of resource shortage, which brings significant challenges to large-scale production.

[0004] Patent application publication CN109734313A discloses an anti-slip antique glaze, which includes the following components by mass: 8.0-11.0 parts of kaolin, 4.3-12.1 parts of calcined kaolin, 3.2-4.0 parts of zircon sand, 27.6-29.5 parts of nepheline, 5.5-15.8 parts of polishing tile powder, 20.7-21.6 parts of wollastonite, 4.8-5.1 parts of magnesium oxide, 2.1-3.6 parts of zinc oxide, 3.2-5.1 parts of quartz sand, 1.6-2.0 parts of iron oxide, 1.3-2.0 parts of copper oxide, 1.5-1.8 parts of chromium oxide, and 0.9-3.0 parts of nickel oxide. The fineness of the glaze is less than 2% after passing through a 10,000-hole sieve. The raw material cost is high and the process is complicated.

[0005] Patent application publication CN109081677A discloses an antique brick body made from high-calcium-magnesium skarn iron tailings. The raw material composition, by weight, is: 20-25 parts skarn iron tailings, 30-40 parts quartz, 35-45 parts purple wood knots, and 6-12 parts talc. While this reduces reliance on high-quality mineral raw materials, the high cost of raw materials remains.

[0006] The existing production process of antique tiles is complicated, which not only increases the production cost, but also has high investment costs, making it difficult to promote on a large scale. The high investment cost not only limits the participation of small businesses, but also to a certain extent limits the competition and development of the antique tile market. Summary of the Invention

[0007] The present invention provides an all-solid waste metallurgical slag antique brick and a preparation method thereof, which solves the problems of complex manufacturing process and high investment cost in the prior art.

[0008] In order to solve the above problems, the present invention provides an all-solid waste metallurgical slag antique brick, which is a brick formed by pressing and molding a composite material of silicon manganese slag and magnesium slag, and the physical phases formed after firing are diopside, magnesia feldspar, calcium ferrite and corundum.

[0009] Through the above scheme, the problems of complex manufacturing process and high investment cost of traditional antique bricks can be effectively solved. Solid waste raw materials such as silicon manganese slag and magnesium slag can be used to prepare all-solid waste metallurgical slag antique bricks, which reduces environmental pollution, lowers production costs, and ultimately achieves a dual improvement in energy conservation, environmental protection and economic benefits.

[0010] Furthermore, in the silicomanganese slag, the mass proportion of magnesium slag does not exceed 70%.

[0011] Furthermore, the mass ratio of the silicomanganese slag to the magnesium slag is 0.4-0.7:0.3-0.6. Preferably, the mass ratio of the silicomanganese slag to the magnesium slag is 0.6:0.4.

[0012] Through the above scheme, we can effectively utilize the two industrial solid waste resources of silicon manganese slag and magnesium slag, and significantly improve the physical and mechanical properties and durability of antique tiles, reduce environmental pollution, and achieve resource recycling and environmental protection goals.

[0013] Furthermore, the firing temperature is 1100°C~1140°C.

[0014] Furthermore, the particle size of the silicomanganese slag is no larger than 100 mesh, and preferably, the particle size of the silicomanganese slag is 100-150 mesh, 150-200 mesh, or no larger than 200 mesh. With the above solution, the smaller the particle size of the silicomanganese slag, the larger the contact area, making the reaction more complete, reducing investment costs, and producing antique tiles that are both environmentally friendly and economical.

[0015] Furthermore, it also includes coal gangue. Adding coal gangue allows the firing process to fully react, which can save energy and consume coal gangue solid waste.

[0016] Furthermore, the coal gangue accounts for 5-16% of the total mass of the solid waste metallurgical slag antique brick raw materials. Preferably, the coal gangue accounts for 10% of the total mass of the solid waste metallurgical slag antique brick raw materials.

[0017] Furthermore, the firing time is 25 min to 45 min, preferably, the firing time is 30 min. The present invention also provides a method for preparing antique bricks made of all-solid waste metallurgical slag, comprising: Mixing dried silicon-manganese slag and magnesium slag in a mass ratio of 0-0.7:1-0.3, and pressing them into green compacts under a load of 8 tons; The green brick is fully fired at 1100° C. to 1140° C. to obtain the antique brick.

[0018] The present invention also provides another method for preparing antique bricks using all-solid waste metallurgical slag, comprising: The dried silico-manganese slag, magnesium slag and coal gangue are pressed into green compacts at a mass ratio of 0-0.7:1-0.3:0.08-0.12 under a load of 8 tons; The green body is fully fired at 1100° C. to obtain antique bricks.

[0019] The technical effects of this application are: 1. The all-solid waste metallurgical slag antique brick adopts waste material ratio and simple preparation process to produce bricks with dense structure, which effectively solves the problems of complex manufacturing process and high investment cost in the existing technology.

[0020] 2. The present invention not only reduces environmental pollution and improves the utilization rate of waste, but also solves the problem of raw material shortage caused by clay resource protection.

[0021] 3. The present invention not only effectively disposes of metallurgical solid waste, bringing a win-win situation to the enterprise, but also enhances the added value of products and significantly increases economic and social benefits.

[0022] 4. Preferably, the present invention also includes coal gangue. Adding coal gangue allows the firing process to fully react, which can save energy and consume coal gangue solid waste. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a physical diagram of the embodiment provided in this application.

[0024] Figure 2 This is the XRD diagram of antique brick microcrystalline glass fired by a combination of silicon manganese slag and magnesium slag. The three curves in the figure represent magnesium slag contents of 30%, 40%, and 50%, respectively.

[0025] Figure 3 These are the test results of water absorption and density performance of antique tile microcrystalline glass at different temperatures.

[0026] Figure 4 These are the test results of the acid resistance of antique tile microcrystalline glass at different temperatures.

[0027] Figure 5 The test results of compressive strength and bending strength of antique tile glass-ceramic at different temperatures Figure 6 XRD patterns of antique brick glass-ceramics fired with different particle sizes of silicon-manganese slag Figure 7 These are the test results of water absorption and density of antique tile microcrystalline glass with different coal gangue addition amounts.

[0028] Figure 8These are the test results of the acid resistance of antique tile microcrystalline glass with different coal gangue addition amounts.

[0029] Figure 9 These are the test results of the compressive strength and flexural strength of antique brick microcrystalline glass with different coal gangue addition amounts.

[0030] Figure 10 This is the XRD diagram of antique brick glass-ceramics with different coal gangue addition amounts. DETAILED DESCRIPTION

[0031] The following embodiments of the technical solution of the present application are described in detail. The following embodiments are only used to more clearly illustrate the technical solution of the present application and are therefore only used as examples and are not intended to limit the scope of protection of the present application.

[0032] The present application provides an all-solid waste metallurgical slag antique brick, which is a pressed and molded product of a composite material of silicon manganese slag and magnesium slag, and the phases formed after firing are diopside, magnesia feldspar, calcium ferrite and corundum.

[0033] The raw materials for the antique tiles include a mass ratio of silicomanganese slag to magnesium slag of 0-0.7:1-0.3, preferably 0.4-0.7:0.3-0.6, and more preferably 0.6:0.4. The particle size of the silicomanganese slag is no larger than 100 mesh, preferably 100-150 mesh, 150-200 mesh, or no larger than 200 mesh.

[0034] The antique brick is prepared by mixing dried silicomanganese slag and magnesium slag in a mass ratio of 0-0.7:1-0.3, pressing the mixture into a green body under a load of 8 tons, and firing the green body at 1100°C-1140°C to obtain the antique brick. The firing time is 25-45 minutes, preferably 30 minutes.

[0035] To lower the sintering temperature, the present invention adds coal gangue to reduce the firing temperature, which not only saves energy but also consumes coal gangue solid waste. The coal gangue accounts for 5-16% of the total mass of the solid waste metallurgical slag antique brick raw materials. Preferably, the coal gangue accounts for 10% of the total mass of the solid waste metallurgical slag antique brick raw materials.

[0036] Specifically, the preparation method of the antique bricks with added coal gangue raw materials is as follows: dry silicomanganese slag, magnesium slag and coal gangue are pressed into green bodies at a mass ratio of 0~0.7:1~0.3:0.08~0.12 under a load of 8t; and the green bodies are fully fired at 1100℃~1140℃ to obtain antique bricks.

[0037] Below, the present invention is described by specific examples and comparative examples, which are as follows: Example 1 The silicon manganese slag (the particle size of the silicon manganese slag is 100 mesh-150 mesh) and magnesium slag raw materials are placed in an oven at 105°C for 6 hours, and then prepared into 6 formulas according to different ratios (the amount of magnesium slag added by mass is 0%, 30%, 40%, 50%, 60%, and 70%), and placed in a ball mill and mixed for 6 hours to ensure that the silicon manganese slag and coal slag are fully mixed.

[0038] The green compact was pressed into a cubic shape under a load of 8 tons.

[0039] The temperature was selected to be 5 temperature gradients (1100℃, 1110℃, 1120℃, 1130℃, 1140℃) and fired for 30min to obtain antique bricks. Figure 1 .

[0040] Figure 2 This is the XRD diagram of antique brick microcrystalline glass fired by a combination of silicon manganese slag and magnesium slag. The three curves in the figure represent magnesium slag contents of 30%, 40%, and 50%, respectively.

[0041] Figure 2 The results show that the main phases of the antique bricks obtained in Example 1 are diopside and magnesia feldspar, and the secondary phases are calcium ferrite and corundum. Figure 2 It can be seen that with the increase of magnesium slag content, there is no obvious change in diopside, but the diffraction peak of magnesia chalcedony is constantly increasing. This is because the chemical formula of magnesia chalcedony is Ca2MgSi2O7, and magnesium slag contains a large amount of magnesium compounds, which provides favorable conditions for the synthesis of magnesia chalcedony, thereby promoting the synthesis of magnesia chalcedony.

[0042] Figure 2 It can be seen that after adding magnesium slag, the diffraction peaks of diopside and magnesia feldspar in the fired antique brick glass-ceramics have undergone tremendous changes. The diopside diffraction peak has weakened, while the magnesia feldspar diffraction peak has strengthened. This is because magnesium slag contains more magnesium compounds, which provides a certain basis for the formation of magnesia feldspar. The addition of magnesium slag promotes the formation of magnesia feldspar.

[0043] Example 2 The antique tile component ratio of silicon manganese slag: magnesium slag = 6:4 (mass ratio) in Example 1 was selected, and the particle size of the silicon manganese slag was 100 mesh-150 mesh; the firing temperature was selected from 5 temperature gradients of 1100°C, 1110°C, 1120°C, 1130°C, and 1140°C, and the firing time was 30 min to obtain antique tiles with sample numbers GM1100, GM1110, GM1120, GM1130, and GM1140. The specific formula is shown in Table 1.

[0044] Table 1 According to Table 1 and Figures 3 to 5 , Figure 3 The test results of water absorption and density of antique tile glass-ceramic are shown below. Figure 3 As can be seen from the graph, as the temperature continues to rise, the density of the experimental sample shows a downward trend. When the firing temperature reaches 1100℃, the sample density reaches a peak value of 2.58 g / cm 3 The overall trend of water absorption is an initial increase followed by a decrease. At 1100°C, the water absorption reaches its optimal value of 4.84%. These changes are due to the gradual transition from a solid phase to a liquid phase within the sample as the temperature rises, increasing the liquid content and resulting in an increase in internal voids. Furthermore, as the temperature rises, the viscosity of the liquid phase decreases, reducing the gas's expansion resistance. Free water and bound water within the sample transform into water vapor, which overflows from the sample, promoting the formation of voids within the sample, resulting in a gradual decrease in sample density and an increase in water absorption.

[0045] Figure 4 The following are the test results for the acid resistance of the experimental samples. As can be seen from the figure, the acid resistance of the samples shows an overall downward trend as the temperature rises. When the temperature reaches 1100°C, the acid resistance of the samples reaches its peak, at 98.34%. This is because as the temperature rises, the interior of the samples gradually transforms into a liquid phase, reducing the resistance to gas expansion. Free and bound water transform into a gaseous state and escape from the sample, creating more voids within the sample. During the acid resistance test, the acid flows into the sample through these voids. The higher the temperature, the more voids there are, increasing the contact area between the sample and the acid, which reduces the acid resistance.

[0046] Figure 5 The following are the test results for the compressive and flexural strengths of antique tile glass-ceramics. As can be seen from the figure, the compressive strength of the experimental samples gradually decreases with increasing temperature, while the flexural strength shows a trend of first increasing and then decreasing with increasing temperature. When the temperature reaches 1100°C, the compressive and flexural strengths reach their maximum values, with a peak compressive strength of 148 MPa and a peak flexural strength of 43 MPa. This phenomenon occurs because as the temperature rises, the thermal motion of the particles within the sample intensifies, increasing the spacing between the particles and weakening the mutual forces between them, resulting in a decrease in the difference between the internal and surface energy of the particles. Therefore, under the action of external forces, the bearing area is limited, leading to stress concentration and a gradual decrease in the compressive and flexural strengths.

[0047] It can be seen that when the mass ratio of silicon manganese slag: magnesium slag = 6:4 and the temperature is 1100℃, the performance of antique tile microcrystalline glass reaches the best.

[0048] Example 3 A 6:4 ratio of silicon-manganese slag to magnesium slag was selected for the antique tile. The firing temperature was 1100°C and the firing time was 30 minutes. The silicon-manganese slag was sieved into three particle sizes: 100-150 mesh, 150-200 mesh, and below 200 mesh, designated D, Z, and X. The samples were labeled D64, Z64, and X64 according to their different ratios. The specific experimental plan is shown in Table 2.

[0049] Table 2 Figure 6 The XRD patterns of antique brick glass-ceramics fired with different silicomanganese slag particle sizes are shown on the left, with Group Z and Group D showing the right. A comparison of the two figures reveals that the particle size of the silicomanganese slag has little effect on the crystalline phase of the antique brick glass-ceramics. Regardless of whether the Z or D group is fired, the primary phases of the antique brick glass-ceramics remain diopside and magnesia feldspar.

[0050] By comparing the data of groups Z64 and D64, it can be found that under the condition of the same ratio of silicomanganese slag and magnesium slag, the content of magnesia feldspar generated by Z64 is much higher than that of D64. This is because the particle size of the silicomanganese slag in group Z is smaller than that in group D. During the reaction process, the contact area between the particles in group Z is larger, and it can react more fully than that in group D.

[0051] Example 4 The inventors found in pilot tests at the factory that the product obtained was not ideal due to the difficulty in strictly controlling production conditions in actual factory production. To address this problem, they chose to add coal gangue to improve product performance. This not only saves energy but also utilizes coal gangue solid waste, as follows: The antique brick component ratio of silicon manganese slag: magnesium slag: coal gangue = 6:4:0.5 ~ silicon manganese slag: magnesium slag: coal gangue = 6:4:2 was selected, the particle size of silicon manganese slag was 100 mesh-150 mesh; the firing temperature was 1100℃, and the firing time was 30min. The antique bricks with sample numbers D6405, D6410, D6415, and D6420 were obtained. The specific formula is shown in Table 5.

[0052] Table 5 Figure 7 This is the test result of water absorption and density of antique tile microcrystalline glass. Figure 7 It can be seen from the figure that with the continuous increase of coal gangue content, the water absorption of antique brick micro-ceramic glass shows a trend of first decreasing and then increasing. When the coal gangue content reaches 10 parts, the water absorption rate of antique brick micro-ceramic glass reaches the optimal value, which is 5.63%. The overall density trend is that it first increases and then decreases. When the coal gangue content reaches 10%, the density reaches its peak value, which is 2.62 g•cm -3The main components of coal gangue are SiO2 and Al2O3, among which Al2O3 helps to increase the melting temperature of antique brick microcrystalline glass. As the content of coal gangue increases, the content of Al2O3 in the antique brick microcrystalline glass also increases, making the internal structure of the antique brick microcrystalline glass denser, the density gradually increasing, and the water absorption rate gradually decreasing; when the content of coal gangue reaches a certain amount, the silicate molten material generated at high temperature is reduced, the viscosity increases, and the viscosity distribution is uneven, which will cause a large number of pores to appear inside the antique brick microcrystalline glass. When measuring the water absorption rate of the sample, these pores will retain some water. The more pores, the more water is retained, and the water absorption rate of the sample gradually increases.

[0053] Figure 8 The results of the acid resistance test show that as the gangue content increases, the acid resistance of the sample increases first and then slowly decreases. When the gangue content reaches 10 parts, the acid resistance of the antique tile micro-ceramic reaches a maximum of 97.4%. The increase in gangue is accompanied by a gradual increase in Al2O3, which reduces the melting temperature of the antique tile micro-ceramic and makes the internal structure of the sample denser. During the acid leaching process, the acid has difficulty penetrating the sample and corroding it, and can only corrode the sample surface. When the gangue content reaches a certain level, as the gangue content continues to increase, Al2O3 also continues to accumulate, and a large number of pores are generated inside the sample. During the acid resistance test, a large amount of acid will slowly penetrate into the antique tile micro-ceramic, increasing the contact area between the sample and the acid and gradually reducing the acid resistance of the antique tile micro-ceramic.

[0054] Figure 9 The microstructure of antique brick glass-ceramics fired at 1100°C with different gangue contents. As can be seen from the figure, as the gangue content increases, the grains inside the antique brick glass-ceramics become more and more obvious, and the gaps between the grains also become larger. When the gangue content reaches 10 parts, the effect is particularly significant. This is because during the firing process of the antique brick glass-ceramics, in addition to the muffle furnace providing heat to the antique brick glass-ceramics, the gangue contained in the sample also provides heat to the antique brick glass-ceramics. The greater the gangue content, the more heat it provides, and the more liquid phase inside the antique brick glass-ceramics will also increase. At the same time, the bound water inside the antique brick glass-ceramics will also be converted into gaseous state and discharged from the interior of the sample, forming small pores inside the sample. The more bound water is discharged, the more voids there will be inside the sample.

[0055] Figure 10XRD patterns of antique brick glass-ceramics fired with different proportions of gangue added. The three curves in the figure represent gangue additions of 0, 10, and 20 parts, respectively. The figure shows that the primary crystalline phases of the antique brick glass-ceramics are diopside and magnesia, with secondary phases being corundum and calcium ferrite. Although the addition of gangue does not change the primary crystalline phases of the antique brick glass-ceramics, the diffraction peak of magnesia increases with increasing gangue addition. This indicates that the primary firing materials of the antique brick glass-ceramics are silico-manganese slag and magnesium slag. As an additive, gangue only affects the content of the substances within the antique brick glass-ceramics, not the types of substances. Adding gangue increases the firing temperature of the antique brick glass-ceramics, promoting the formation of magnesia. Therefore, the greater the amount of gangue added, the stronger the diffraction peak of magnesia.

[0056] In summary, the performance of antique tile microcrystalline glass reaches the best when the mass ratio of silicon manganese slag: magnesium slag: coal gangue = 6:4:1.

[0057] The above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, a person skilled in the art should understand that the technical solutions described in the aforementioned embodiments can still be modified, or some or all of the technical features therein can be replaced by equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A solid waste metallurgical slag antique brick, characterized in that: The antique brick is a brick whose physical phases are diopside, magnesia feldspar, calcium ferrite and corundum formed by pressing and molding a composite material of silicon manganese slag and magnesium slag and then firing.

2. The all-solid waste metallurgical slag antique brick according to claim 1, characterized in that: In the silicon-manganese slag, the mass proportion of magnesium slag does not exceed 70%.

3. The all-solid waste metallurgical slag antique brick according to claim 2, characterized in that: The mass ratio of the silicomanganese slag to the magnesium slag is 0.4-0.7:0.3-0.

6. Preferably, the mass ratio of the silicomanganese slag to the magnesium slag is 0.6:0.

4.

4. The all-solid waste metallurgical slag antique brick according to claim 1, characterized in that: The firing temperature is 1100°C to 1140°C.

5. The all-solid waste metallurgical slag antique brick according to claim 1, characterized in that: The particle size of the silicomanganese slag is not greater than 100 mesh. Preferably, the particle size of the silicomanganese slag is 100 mesh-150 mesh, 150 mesh-200 mesh, and not greater than 200 mesh.

6. The all-solid waste metallurgical slag antique brick according to claim 1, characterized in that: Also includes coal gangue.

7. The all-solid waste metallurgical slag antique brick according to claim 6, characterized in that: The coal gangue accounts for 5-16% of the total mass of the solid waste metallurgical slag antique brick raw materials. Preferably, the coal gangue accounts for 10% of the total mass of the solid waste metallurgical slag antique brick raw materials.

8. The all-solid waste metallurgical slag antique brick according to claim 1, characterized in that: The firing time is 25 min to 45 min, preferably, the firing time is 30 min.

9. A method for preparing antique bricks made of all-solid waste metallurgical slag, characterized in that: include: Mixing dried silicon-manganese slag and magnesium slag in a mass ratio of 0-0.7:1-0.3, and pressing them into green compacts under a load of 8 tons; The green brick is fully fired at 1100° C. to 1140° C. to obtain the antique brick.

10. A method for preparing antique bricks made of all-solid waste metallurgical slag, characterized in that: include: The dried silico-manganese slag, magnesium slag and coal gangue are pressed into green compacts at a mass ratio of 0-0.7:1-0.3:0.08-0.12 under a load of 8 tons; The green body is fully fired at 1100° C. to obtain antique bricks.

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