Preparation method of new type of foamed ceramic material based on granite marble tailings

Abstract

This invention provides a method for preparing a novel foam ceramic material based on granite and marble tailings, comprising the following steps: S1, mixing granite powder, marble powder, waste glass powder, and additives uniformly to form a mixture; S2, ball milling the mixture to obtain a refined mixture; S3, drying and shaping the refined mixture to obtain a foam ceramic green body; S4, sintering the foam ceramic green body to obtain the novel foam ceramic material based on granite and marble tailings. This invention uses waste as the main component, transforming accumulated waste into economically beneficial products, achieving green and low-carbon industrial development, and possessing advantages such as high ecological value and good economic benefits. The lightweight foam ceramic obtained by this invention has excellent compressive strength and achieves large-scale disposal of solid waste, overcoming the problems existing in the prior art.

Description

Technical Field

[0001] This invention relates to the field of building materials technology, specifically to a method for preparing a novel foam ceramic material based on granite and marble tailings. Background Technology

[0002] Traditional foamed ceramics are mostly made from clay, feldspar, and other raw materials, which is not only energy-intensive and costly but also consumes a large amount of high-quality mineral resources. With the rapid development of industry and construction, the demand for building materials such as stone continues to grow, resulting in a significant increase in industrial solid waste such as granite powder, marble powder, and glass powder. Statistics show that the processing of granite and marble slabs generates a large amount of waste powder, exceeding 30% of the raw materials. Traditional landfill disposal of solid waste not only occupies a large amount of land and involves a lot of engineering work but also causes serious environmental pollution. However, recycled waste soda-lime glass powder, due to its compositional characteristics, exhibits unique value in the preparation of foamed ceramics. The high silica content in soda-lime glass can serve as a silicon-based framework for foamed ceramics, while the sodium oxide, calcium oxide, and other metal oxides it contains can effectively lower the melting temperature of the mixture, reducing energy consumption.

[0003] Against the backdrop of increasingly stringent market requirements for the performance and environmental friendliness of building materials, traditional ceramic materials suffer from drawbacks such as heavy weight and insufficient thermal insulation. In contrast, foamed ceramics, as a new type of green building material, offer advantages such as lightweight, thermal insulation, sound insulation, and fire resistance, attracting widespread attention. Therefore, developing a foamed ceramic material using industrial waste or common mineral powders as raw materials is of significant practical importance. Summary of the Invention

[0004] To address the shortcomings and deficiencies of existing technologies, this invention provides a method for preparing a novel foamed ceramic material based on granite and marble tailings. The foamed ceramic of this invention uses waste powder from granite and marble processing and recycled waste sodium-calcium glass powder as main raw materials, adds additives, and is then sintered at high temperature in a kiln. After cutting and polishing, it becomes a lightweight, heat-insulating, and sound-insulating ceramic building material. This invention uses waste as the main component, transforming accumulated waste into economically beneficial products, achieving green and low-carbon industrial development, and possessing advantages such as high ecological value and good economic benefits. The lightweight foamed ceramic obtained by this invention has excellent compressive strength and achieves large-scale disposal of solid waste, overcoming the problems existing in existing technologies.

[0005] One object of the present invention is to provide a method for preparing a novel foam ceramic material based on granite and marble tailings, the method comprising the following steps: S1. Mix granite powder, marble powder, waste glass powder and additives evenly to prepare a mixture; S2. The mixture is subjected to wet ball milling to obtain a refined mixture; S3. The refined mixture is dried and shaped to obtain a foam ceramic green body; S4. The foam ceramic green body is sintered to obtain a new type of foam ceramic material based on granite and marble tailings.

[0006] Furthermore, the additive is selected from one or more of auxiliary foaming agents and foam stabilizers.

[0007] Furthermore, the auxiliary foaming agent is silicon carbide, and the foam stabilizer is sodium phosphate.

[0008] Furthermore, the mass ratio of the auxiliary foaming agent to the foam stabilizer is (0.01-2):(1-5).

[0009] Furthermore, the mass ratio of the granite powder, marble powder, waste glass powder and additives is (50-60):(20-30):(10-30):(1-10).

[0010] Furthermore, the waste glass powder is waste sodium-calcium glass powder.

[0011] Furthermore, the ball milling adopts a wet ball milling process, in which an organic binder is added, and the particle size of the refined mixture is 100-200 mesh.

[0012] Furthermore, ethanol is added as an organic binder in the wet ball milling process.

[0013] Furthermore, the drying and shaping temperature is 50-70℃, and the time is 2-5 hours.

[0014] Furthermore, the sintering temperature is 1050-1250℃ and the time is 30-90 min.

[0015] Furthermore, the granite powder, by mass percentage, has the following composition: SiO2: 50-70wt%, Al2O3: 20-30wt%, Na2O+K2O: 5-10wt%, CaO+MgO: 1-5wt%, Fe2O3: 0-3wt%; the marble powder, by mass percentage, has the following composition: CaO: 80-98wt%, MgO+Fe2O3: 0-2wt%, Al2O3+Na2O+K2O: 1-5wt%.

[0016] Furthermore, the waste sodium-calcium glass powder, by mass percentage, has the following composition: SiO2: 70-90wt%, Al2O3: 0-3wt%, Na2O+K2O: 0-3wt%, CaO+MgO: 5-15wt%.

[0017] Further, the sintering step includes: sequentially performing a first heating, a first holding, a second heating, a third heating, a second holding, a cooling, and a third holding. The target temperature for the first heating is 500℃, with a heating rate of 6℃ / min-11℃ / min; the temperature for the first holding is 500℃, with a holding time of 30 min-60 min; the target temperature for the second heating is 800℃, with a heating rate of 5℃ / min-8℃ / min; the target temperature for the third heating is 1050℃-1250℃, with a heating rate of 3℃ / min-6℃ / min; the temperature for the second holding is the target temperature for the third heating, with a holding time of 30 min-90 min; the cooling rate is 2℃ / min-5℃ / min, with the target temperature being the temperature of the third holding; the temperature for the third holding is 600℃, with a holding time of 30 min-90 min, followed by natural cooling to room temperature.

[0018] Specifically, the primary purpose of the first heating and first holding stages is to remove surface water, bound water, and some impurities from the raw materials. Rapid heating and holding are employed to ensure thorough removal, thereby improving the purity of the foam ceramic and activating the raw materials. The second heating rate is appropriately reduced to promote the formation of a low-temperature eutectic liquid phase, laying the foundation for the subsequent foaming process. The third heating and second holding stage is the core sintering stage. By reducing the heating rate and holding for a sufficient time, it ensures that the foaming agent and foam stabilizer fully interact, generating a large number of uniformly distributed bubbles in the eutectic liquid phase, forming a stable pore structure. The final cooling and third holding stages aim to achieve controllable and uniform cooling of the system, reducing or eliminating the inherent structural stress of the material and preventing cracking or breakage of the foam ceramic.

[0019] Another objective of this invention is to provide the application of the above-mentioned method for preparing novel foam ceramic materials based on granite and marble tailings in building materials.

[0020] The present invention has the following beneficial effects: This invention uses granite waste, marble waste, and recycled waste glass as main raw materials to prepare foamed ceramics, realizing the synergistic recycling of multiple solid wastes and effectively solving the problem of large-scale land occupation and heavy pollution caused by the accumulation of building material waste in the local area. The technical solution of this invention aligns with the needs of the building materials industry chain, turning waste into treasure and creating economic benefits while controlling pollution. Through optimized distribution ratios of the various waste components, the resulting foamed ceramics exhibit a more uniform pore structure and significantly improved compressive strength.

[0021] Specifically, the SiO2 abundant in granite powder and waste soda-lime glass powder can form a large amount of liquid phase under high temperature conditions, constituting the main framework of foam ceramics. Simultaneously, the Al2O3 contained in the granite powder can improve the structural stability and viscosity of the liquid phase, enhancing the melt's resistance to flow, thus promoting the stable existence of bubbles and inhibiting their coalescence and collapse. An appropriate amount of CaO can form a eutectic system with SiO2 and Al2O3, lowering the sintering temperature and improving the liquid phase's fluidity, making the foaming process more controllable. The K2O and Na2O in the waste soda-lime glass powder further act as network modifiers, effectively regulating the liquid phase viscosity and promoting the uniform generation and distribution of bubbles.

[0022] The main component of marble waste is CaCO3, which acts as both a primary foaming agent and flux, decomposing at high temperatures to release CO2 gas. With the synergistic effect of the foam stabilizer Na3PO4, uniform and stable bubble structures are formed within a liquid phase system of suitable viscosity and surface tension resulting from the aforementioned specific components. Therefore, only when the components such as SiO2, Al2O3, and CaO in the granite powder are within a reasonable ratio range can a synergistic match between liquid phase formation, bubble generation, and stabilization be achieved, ultimately resulting in foam ceramics with high porosity, uniform structure, and high compressive strength.

[0023] The foam ceramic prepared by this invention possesses excellent properties such as lightweight, sound insulation, heat insulation, and fire resistance. By introducing a rich and uniform porous structure, the foam ceramic can reduce its weight by 10-30% for the same volume, making it suitable for non-load-bearing wall decoration, panels, partitions, and other applications. Furthermore, its low cost, superior performance, and high strength provide the building materials market with new material options, enriching the product range and meeting the demand for high-quality, affordable products. Attached Figure Description

[0024] Figure 1 The surface morphology of the novel foam ceramic material based on granite and marble tailings prepared in Example 1 is shown.

[0025] Figure 2 The surface morphology of the novel foam ceramic material based on granite and marble tailings prepared in Example 2 is shown.

[0026] Figure 3 The surface morphology of the novel foam ceramic material based on granite and marble tailings prepared in Example 3 is shown.

[0027] Figure 4 The surface morphology of the foam ceramic material prepared in a comparative example is shown. Detailed Implementation

[0028] To more clearly illustrate the technical solution of the present invention, the following embodiments are provided. Unless otherwise stated, the raw materials, reactions, and post-processing methods appearing in the embodiments are all commercially available raw materials and technical methods well known to those skilled in the art.

[0029] The terms "preferred," "more preferably," and "more suitable" used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0030] It should be understood that, except in any operational instance or otherwise indicated, the amounts or all figures representing ingredients used, for example, in the specification and claims, should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise stated, the numerical parameters set forth in the following specification and appended claims are approximate values ​​varying according to the desired performance to be obtained according to the invention.

[0031] The main chemical composition of the waste granite powder in this embodiment of the invention, by mass percentage, is as follows: SiO2 61.80 wt%, Al2O3 26.57 wt%, Na2O 2.29 wt%, K2O 4.60 wt%, CaO 3.87 wt%, MgO 0.15 wt%, and Fe2O3 0.13 wt%.

[0032] In this embodiment of the invention, the auxiliary foaming agent is silicon carbide, and the foam stabilizer is sodium phosphate, both purchased from Aladdin Reagent Company.

[0033] The main chemical composition of the marble powder in this embodiment of the invention, by mass percentage, is as follows: SiO2 0.55 wt%, Al2O3 0.09 wt%, Na2O 0.18 wt%, K2O 0.05 wt%, CaO 96.96 wt%, MgO 1.93 wt%, and Fe2O3 0.05 wt%.

[0034] The main chemical composition of the waste sodium-calcium glass powder in this embodiment of the invention, by mass percentage, is as follows: SiO2 84.55 wt%, Al2O3 0.59 wt%, Na2O 0.52 wt%, K2O 0.10 wt%, CaO 9.71 wt%, MgO 4.29 wt%, and Fe2O3 0.11 wt%.

[0035] In the embodiments of this invention, "parts" refers to parts by weight.

[0036] Example 1 A method for preparing a novel foamed ceramic material based on granite and marble tailings, the method comprising the following steps: S1. After drying the granite powder, soda-lime glass powder and marble powder, mix 60 parts of granite powder, 30 parts of marble powder, 10 parts of soda-lime glass powder, 1 part of auxiliary foaming agent and 5 parts of foam stabilizer evenly to obtain a mixture. S2. Add the mixture to a ball mill, add 30 parts of ethanol, and ball mill using a wet process for 2 hours to obtain a refined mixture; S3. The refined mixture is poured into a mold and dried at 50°C for 3 hours to solidify, thus obtaining a foam ceramic green body; S4. The foam ceramic green body is placed in a sintering furnace for sintering treatment. The specific sintering steps are as follows: the first stage of heating is carried out at a heating rate of 10℃ / min, with a target temperature of 500℃, and the temperature is held at 500℃ for 30 min; then the second stage of heating is carried out at a heating rate of 8℃ / min, with a target temperature of 800℃; then the third stage of heating is carried out at a heating rate of 5℃ / min, with a target temperature of 1150℃, and the temperature is held at 1150℃ for 30 min; after calcination, the temperature is controlled to drop to 600℃ at a cooling rate of 5℃ / min, and then held for 30 min, and then naturally cooled to obtain a new type of foam ceramic material based on granite and marble tailings.

[0037] Figure 1 The surface morphology of the novel foam ceramic material based on granite and marble tailings prepared in Example 1 is shown, with an outer diameter of 39 mm.

[0038] Example 2 A method for preparing a novel foamed ceramic material based on granite and marble tailings, the method comprising the following steps: S1. After drying the granite powder, soda-lime glass powder and marble powder, mix 60 parts of granite powder, 10 parts of marble powder, 30 parts of soda-lime glass powder and 5 parts of foam stabilizer evenly to obtain a mixture. S2. Add the mixture to a ball mill, add 30 parts of ethanol, and ball mill using a wet process for 2 hours to obtain a refined mixture; S3. The refined mixture is poured into a mold and dried at 50°C for 3 hours to solidify, thus obtaining a foam ceramic green body; S4. The foam ceramic green body is placed in a sintering furnace for sintering treatment. The specific sintering steps are as follows: the first stage of heating is carried out at a heating rate of 10℃ / min, with a target temperature of 500℃, and the temperature is held at 500℃ for 30 min; then the second stage of heating is carried out at a heating rate of 8℃ / min, with a target temperature of 800℃; then the third stage of heating is carried out at a heating rate of 5℃ / min, with a target temperature of 1150℃, and the temperature is held at 1150℃ for 30 min; after calcination, the temperature is controlled to drop to 600℃ at a cooling rate of 5℃ / min, and then held for 30 min, and then naturally cooled to obtain a new type of foam ceramic material based on granite and marble tailings.

[0039] Figure 2 The surface morphology of the novel foam ceramic material based on granite and marble tailings prepared in Example 2 is shown, with an outer diameter of 21 mm.

[0040] Example 3 A method for preparing a novel foamed ceramic material based on granite and marble tailings, the method comprising the following steps: S1. After drying the granite powder, soda-lime glass powder and marble powder, mix 60 parts of granite powder, 10 parts of marble powder, 30 parts of soda-lime glass powder, 1 part of auxiliary foaming agent and 10 parts of foam stabilizer evenly to obtain a mixture. S2. Add the mixture to a ball mill, add 30 parts of ethanol, and ball mill using a wet process for 2 hours to obtain a refined mixture; S3. The refined mixture is poured into a mold and dried at 50°C for 3 hours to solidify, thus obtaining a foam ceramic green body; S4. The foam ceramic green body is placed in a sintering furnace for sintering treatment. The specific sintering steps are as follows: the first stage of heating is carried out at a heating rate of 10℃ / min, with a target temperature of 500℃, and the temperature is held at 500℃ for 30 min; then the second stage of heating is carried out at a heating rate of 8℃ / min, with a target temperature of 800℃; then the third stage of heating is carried out at a heating rate of 5℃ / min, with a target temperature of 1150℃, and the temperature is held at 1150℃ for 30 min; after calcination, the temperature is controlled to drop to 600℃ at a cooling rate of 5℃ / min, and then held for 30 min, and then naturally cooled to obtain a new type of foam ceramic material based on granite and marble tailings.

[0041] Figure 3 The surface morphology of the novel foam ceramic material based on granite and marble tailings prepared in Example 3 is shown, with an outer diameter of 28 mm.

[0042] Comparative Example The difference between this comparative example and Example 1 is that in step S1, granite powder is replaced with SiO2 (purchased from Aladdin Reagent Company), while other materials and preparation methods are the same as in Example 1.

[0043] Specifically, the comparative preparation method includes the following steps: S1. After drying the SiO2 reagent, soda-lime glass powder and marble powder, mix 60 parts of SiO2 reagent, 30 parts of marble powder, 10 parts of soda-lime glass powder, 1 part of auxiliary foaming agent and 5 parts of foam stabilizer evenly to obtain a mixture. S2. Add the mixture to a ball mill, add 30 parts of ethanol, and ball mill using a wet process for 2 hours to obtain a refined mixture; S3. The refined mixture is poured into a mold and dried at 50°C for 3 hours to solidify, thus obtaining a foam ceramic green body; S4. The foam ceramic green body is placed in a sintering furnace for sintering treatment. The specific sintering steps are as follows: the first stage of heating is carried out at a heating rate of 10℃ / min, with a target temperature of 500℃, and the temperature is held at 500℃ for 30 min; then the second stage of heating is carried out at a heating rate of 8℃ / min, with a target temperature of 800℃; then the third stage of heating is carried out at a heating rate of 5℃ / min, with a target temperature of 1150℃, and the temperature is held at 1150℃ for 30 min; after calcination, the temperature is controlled to drop to 600℃ at a cooling rate of 5℃ / min, and held for 30 min, and then naturally cooled to obtain the foam ceramic material.

[0044] Figure 4 The surface morphology of the comparatively prepared foam ceramic material is shown, with an outer diameter of 12 mm.

[0045] Test case The samples prepared in the examples and comparative examples were subjected to performance tests.

[0046] Test method reference: GB / T 33500-2017 Foamed Ceramics for External Wall Insulation GB / T 29416-2012 Test Methods for Fire Resistance Performance of External Thermal Insulation Systems for Buildings The test results are shown in Table 1.

[0047] Table 1 Performance Test Results As shown in Table 1, under the same firing regime, replacing granite powder with silica reagent alters the liquid phase formation behavior and high-temperature viscosity window due to the lack of beneficial components such as Al2O3, CaO, K2O, and Na2O provided by granite powder. This makes it difficult to achieve an effective match between gas evolution and melt encapsulation, resulting in a decrease in the foaming degree, poorer pore structure uniformity, and lower closed-cell rate of the obtained foam ceramic. Consequently, the comparative sample exhibits increased bulk density, decreased compressive strength, and increased water absorption, indicating that the granite powder of this invention cannot be replaced by other substances such as SiO2; only its specific multi-component composition can achieve the desired technical effect.

[0048] Under fire resistance test conditions, when silica reagent was used to replace granite powder, the resulting foamed ceramic still exhibited non-combustible properties, with its combustion performance rating remaining essentially unchanged. However, due to the lack of synergistic regulatory effects of components such as Al2O3, CaO, and alkali metal oxides on high-temperature structural stability and pore structure formation, the material's pore structure uniformity decreased, closed-cell rate decreased, and thermal conductivity increased. Under flame conditions, heat was more easily conducted to the unexposed surface, and the material's structural stability at high temperatures weakened, making it prone to localized cracking or collapse. This resulted in reduced thermal insulation performance and fire resistance integrity, manifested as increased temperature rise on the unexposed surface and shortened fire resistance time. This indicates that the multi-component composition of granite powder plays a crucial role in improving the overall fire resistance performance of foamed ceramics.

[0049] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0050] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A method for preparing a novel foam ceramic material based on granite and marble tailings, characterized in that, The preparation method of the novel foam ceramic material based on granite and marble tailings includes the following steps: S1. Mix granite powder, marble powder, waste glass powder and additives evenly to prepare a mixture; S2. The mixture is ball-milled to obtain a refined mixture; S3. The refined mixture is dried and shaped to obtain a foam ceramic green body; S4. The foam ceramic green body is sintered to obtain a new type of foam ceramic material based on granite and marble tailings.

2. The preparation method of the novel foam ceramic material based on granite and marble tailings according to claim 1, characterized in that, The additives are selected from one or more of auxiliary foaming agents and foam stabilizers.

3. The preparation method of the novel foam ceramic material based on granite and marble tailings according to claim 2, characterized in that, The auxiliary foaming agent is silicon carbide, and the foam stabilizer is sodium phosphate.

4. The preparation method of the novel foam ceramic material based on granite and marble tailings according to claim 2, characterized in that, The mass ratio of the auxiliary foaming agent to the foam stabilizer is (0.01-2):(1-5).

5. The preparation method of the novel foam ceramic material based on granite and marble tailings according to claim 1, characterized in that, The mass ratio of the granite powder, marble powder, waste glass powder and additives is (50-60):(20-30):(10-30):(1-10).

6. The preparation method of the novel foam ceramic material based on granite and marble tailings according to claim 1, characterized in that, The waste glass powder is waste sodium-calcium glass powder.

7. The preparation method of the novel foam ceramic material based on granite and marble tailings according to claim 1, characterized in that, The ball milling adopts a wet ball milling process, in which an organic binder is added, and the particle size of the refined mixture is 100-200 mesh.

8. The preparation method of the novel foam ceramic material based on granite and marble tailings according to claim 1, characterized in that, The drying and shaping temperature is 50-70℃, and the time is 2-5 hours.

9. The preparation method of the novel foam ceramic material based on granite and marble tailings according to claim 1, characterized in that, The sintering temperature is 1050-1250℃ and the time is 30-90 min.

10. The application of the preparation method of the novel foam ceramic material based on granite and marble tailings as described in any one of claims 1-9 in building materials.

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