A ceramic body based on lithium tailings, ceramic tile and method for its preparation

Abstract

The application discloses a kind of ceramic blank based on lithium tailings, according to mass fraction calculation, the raw materials of the ceramic blank include ball clay 25~35 parts, lithium tailings 50~70 parts, wollastonite 1~5 parts and zircon frit 5~10 parts;Wherein, the chemical composition of the lithium tailings includes potassium oxide and sodium oxide;The crystal structure of the wollastonite is acicular crystal structure;The raw material of the zircon frit includes alumina, quartz, composite zircon, potassium feldspar and sodium feldspar.A kind of ceramic blank based on lithium tailings is proposed in the present application, under the premise of a large amount of lithium tailings, ensuring to reduce the calcination temperature and calcination time of ceramic blank, to overcome the deficiencies in the prior art, improve the strength and whiteness.

Description

Technical Field

[0001] This invention relates to the field of ceramic technology, and in particular to a ceramic blank, ceramic brick and its preparation method based on lithium tailings. Background Technology

[0002] Lithium tailings, as industrial waste generated during lithium material production, are closely related to the rapid development of the lithium materials industry. For every ton of lithium carbonate produced, eight to ten tons of lithium tailings are generated. With the surge in market demand for lithium materials, the output of lithium tailings has been increasing year by year. However, lithium tailings themselves have low utilization value and are forced to be stockpiled due to difficulties in effective utilization. This disposal method not only occupies a large amount of land resources but also poses a potential threat to the ecological environment.

[0003] Therefore, the efficient utilization and proper treatment of lithium tailings has become an urgent problem to be solved. Lithium tailings contain potassium oxide and sodium oxide, which have fluxing properties, giving them a good fluxing effect. To reduce the production cost of ceramic bricks and improve the utilization rate of lithium tailings, existing technologies add lithium tailings to the ceramic raw material formula. Utilizing the fluxing effect of lithium tailings, the calcination temperature and time of the ceramic raw material are reduced, achieving low-cost, green production and enhancing the competitiveness of ceramic products.

[0004] However, due to the inherent limitations of lithium tailings, adding large amounts of lithium tailings to the formula can easily lead to a significant reduction in the strength of ceramic bricks.

[0005] Specifically, the large addition of lithium tailings to the formula also means that the content of potassium oxide and sodium oxide in the ceramic body formula is high. Since potassium oxide and sodium oxide have a large coefficient of thermal expansion, the large use of lithium tailings can easily lead to excessive shrinkage during the calcination process of the ceramic body, resulting in cracks in the obtained ceramic body and affecting its structural strength.

[0006] In addition, due to the fluxing effect of lithium tailings, the large amount of lithium tailings added to the formula will significantly reduce the calcination temperature of the ceramic blank. When the calcination temperature of the ceramic blank is too low, the moisture and gas generated during the calcination process cannot be completely removed in time, which can easily make the internal structure of the calcined ceramic blank loose, and further lead to a decrease in the strength of the ceramic blank. Summary of the Invention

[0007] The purpose of this invention is to propose a ceramic blank based on lithium tailings, which improves strength and whiteness while making extensive use of lithium tailings and ensuring a reduction in the calcination temperature and time of the ceramic blank, thereby overcoming the shortcomings of the prior art.

[0008] The second objective of this invention is to provide a method for preparing ceramic tiles. The method is simple and easy to operate, which solves the problem that the large-scale use of lithium tailings in the prior art leads to a decrease in the strength of ceramic tiles. At the same time, it improves the whiteness of ceramic tiles and ensures the decorative effect of ceramic tiles.

[0009] The third objective of this invention is to provide a ceramic tile prepared by the above-mentioned method, which has a modulus of rupture ≥32MPa and a breaking strength ≥2000N, and has high strength while ensuring the decorative effect of the ceramic tile.

[0010] To achieve this objective, the present invention adopts the following technical solution:

[0011] A ceramic blank based on lithium tailings, wherein the raw materials of the ceramic blank, calculated by mass parts, include 25-35 parts of clay, 50-70 parts of lithium tailings, 1-5 parts of wollastonite, and 5-10 parts of zirconium frit; wherein the chemical composition of the lithium tailings includes potassium oxide and sodium oxide; and the crystal structure of the wollastonite is a needle-like crystal structure.

[0012] The raw materials for the zirconium ingot include alumina, quartz, composite zirconium, potassium feldspar, and sodium feldspar.

[0013] Furthermore, according to the mass fractions, the raw materials of the zircon frit include 25-35 parts of alumina, 15-23 parts of quartz, 18-22 parts of composite zirconium, 15-23 parts of potassium feldspar, and 8-13 parts of sodium feldspar; and according to the mass ratio, the mixing ratio of alumina to quartz is (1.5-2):1.

[0014] Furthermore, the whiteness of the composite zirconium is ≥60°, the whiteness of the ball soil is ≥65°, and the whiteness of the wollastonite is ≥60°.

[0015] Furthermore, the lithium tailings include the Dafu lithium tailings and the Shimen medium-temperature sand lithium tailings;

[0016] The chemical composition of the Dafu lithium tailings, calculated by mass percentage, includes SiO2 78.69–78.77%, Al2O3 12.43–12.70%, Fe2O3 0.08–0.15%, TiO2 0–0.02%, CaO 0.30–0.60%, MgO 0.06–0.08%, K2O 2.36–2.56%, and Na2O 4.58–4.68%, with the remainder being loss on ignition.

[0017] The chemical composition of the Shimen medium-temperature lithium tailings, calculated by mass percentage, includes SiO2 69.52–69.60%, Al2O3 18.68–18.72%, Fe2O3 0.43–0.53%, TiO2 0.02–0.06%, CaO 0.78–0.10%, MgO 0.15–0.21%, K2O 2.53–2.78%, Na2O 4.12–4.32%, and Li2O 0.24–0.30%, with the remainder being loss on ignition.

[0018] Furthermore, the particle size of the Dafu lithium tailings is ≤1cm, and the whiteness is 50-58°;

[0019] The particle size of the medium-temperature lithium tailings from the Shimen mine is ≤2cm, and the whiteness is 20-25°.

[0020] Furthermore, based on the mass ratio, the mixing ratio of the Dafu lithium tailings and the Shimen medium-temperature sand lithium tailings is (1-2):1.

[0021] A method for preparing ceramic bricks, using the lithium tailings-based ceramic blanks described above, includes the following steps:

[0022] A. Mix the alumina, quartz, composite zircon, potassium feldspar and sodium feldspar in the specified amounts evenly, calcine and quench in water to obtain zircon frit;

[0023] B. Mix the formula-formulated clay, lithium tailings, wollastonite and zirconium frit evenly to obtain a lithium tailings-based ceramic blank;

[0024] C. The blank is rolled into a ceramic blank and dried to obtain a ceramic body.

[0025] D. The ceramic bricks are calcined in a kiln and then polished to obtain ceramic bricks; wherein the calcination temperature is 1100-1140℃ and the calcination time is 35-40min.

[0026] Furthermore, in step C, the drying temperature is 170–190°C, and the drying time is 30–60 min.

[0027] Further, in step A, the firing curve of the zirconium ingot is as follows:

[0028] (1) It takes 1 to 3 hours to heat the temperature from room temperature to 500℃;

[0029] (2) The temperature rises from 500℃ to 1100℃ in 0.5 to 1.5 hours;

[0030] (3) The temperature rises from 1100℃ to 1500℃ in 0.5 to 1.5 hours;

[0031] (4) 1500℃, keep warm for 0.5~1h.

[0032] A ceramic tile, prepared using the above-described method for preparing ceramic tiles, wherein the ceramic tile has a modulus of rupture ≥32MPa and a breaking strength ≥2000N.

[0033] The technical solutions provided in this application embodiment may include the following beneficial effects:

[0034] 1. This technical solution utilizes the synergy of zirconium frit and clay to enhance the strength of the ceramic green body. This synergy ensures and improves the strength of the ceramic green body even with the use of large quantities of lithium tailings and reduced calcination temperature and time. Furthermore, the zirconium frit in this solution possesses high toughness, preventing brittle fracture under significant impact or stress, which could drastically reduce the strength of the ceramic green body. In addition, the stable chemical composition of the clay, unaffected by external environmental influences, ensures the stability of its properties during calcination, guaranteeing the long-term strength of the ceramic green body. Moreover, the high whiteness of the clay imparts a high whiteness to the ceramic green body, which, combined with the high whiteness of the zirconium frit, further enhances the whiteness of the ceramic green body.

[0035] 2. The chemical components of wollastonite, silicon dioxide and calcium oxide, provide a low coefficient of thermal expansion and good thermal shock resistance, thereby reducing the shrinkage rate of ceramic green bodies during calcination. Simultaneously, the fine particle size of the clay allows it to form a dense packing when mixed with other raw materials, reducing porosity and effectively minimizing shrinkage during calcination. Furthermore, zirconium frit helps reduce the coefficient of thermal expansion of the ceramic green body, meaning it helps reduce shrinkage during the calcination process. Through the synergistic effect of wollastonite, clay, and zirconium frit, the shrinkage rate of the ceramic green body during calcination is significantly reduced, thus preventing cracking in the resulting ceramic green body and ensuring its strength.

[0036] 3. The needle-like crystal structure of wollastonite provides channels for the release of moisture and gases generated during the calcination of ceramic green bodies, allowing for rapid removal of these substances and preventing the internal structure of the ceramic green body from becoming porous, which would lead to a decrease in strength. Simultaneously, wollastonite also facilitates rapid preheating and cooling processes, contributing to low-temperature, rapid firing. Furthermore, wollastonite has good whiteness, which helps improve the whiteness of the ceramic green body. Detailed Implementation

[0037] This technical solution provides a ceramic blank based on lithium tailings. The raw materials of the ceramic blank, calculated by mass, include 25-35 parts of clay, 50-70 parts of lithium tailings, 1-5 parts of wollastonite, and 5-10 parts of zirconium frit. The lithium tailings contain potassium oxide and sodium oxide. The wollastonite has a needle-like crystal structure.

[0038] The raw materials for the zirconium ingot include alumina, quartz, composite zirconium, potassium feldspar, and sodium feldspar.

[0039] To address the technical problem in existing technologies where strength cannot be guaranteed even with the extensive use of lithium tailings and reductions in calcination temperature and time of ceramic blanks, this invention proposes a ceramic blank based on lithium tailings. The raw materials include clay, lithium tailings, wollastonite, and zircon frit. The zircon frit is made from alumina, quartz, composite zircon, potassium feldspar, and sodium feldspar.

[0040] Firstly, the raw materials for zircon frit include alumina, quartz, composite zirconium, potassium feldspar, and sodium feldspar. Composite zirconium is composed of alumina and zirconium oxide. Since both alumina and zirconium oxide possess high hardness, the composite zirconium exhibits high hardness. Simultaneously, during the high-temperature calcination of the zircon frit, zirconium oxide transforms from a monoclinic phase to a more ductile cubic phase. This phase transformation leads to lattice volume expansion, forming a compressible solid solution. This compressible solid solution can generate a stress field on cracks, inhibiting crack propagation and thus endowing the composite zirconium with extremely high toughness. Therefore, adding composite zirconium to the zircon frit formulation is beneficial for improving the toughness and strength of the zirconium frit. Furthermore, composite zirconium has high whiteness, and adding it to the zircon frit formulation also helps to improve the whiteness of the zirconium frit. In addition, compared to simply adding zirconium oxide to the zircon frit formulation, composite zirconium helps to ensure the strength of the zirconium frit while reducing costs. It should be noted that the composite zirconium in this technical solution is manufactured by Yifeng County Huaqiang Inorganic Materials Co., Ltd., and the model is Composite Zirconium 50.

[0041] Meanwhile, the raw materials for zirconium frit also include alumina and quartz. Quartz's main component is silicon dioxide. The silicon dioxide in alumina and quartz react to form mullite. Mullite possesses excellent high-temperature strength and a low coefficient of thermal expansion, endowing the zirconium frit with high strength and a low coefficient of expansion, thus helping to reduce the coefficient of expansion of ceramic blanks and improve their strength. Simultaneously, mullite also exhibits excellent thermal shock resistance, allowing ceramic blanks to withstand and adapt to rapid preheating and cooling processes, which is beneficial for low-temperature rapid firing.

[0042] In addition, the raw materials for zircon frit also include potassium feldspar and sodium feldspar. Both potassium feldspar and sodium feldspar have a fluxing effect. They can not only reduce the calcination temperature and calcination time of zircon frit and promote the sintering of zircon frit, but also help promote the rapid low-temperature sintering of ceramic blanks.

[0043] Therefore, this technical solution utilizes the combined effects of alumina, quartz, composite zirconium, potassium feldspar, and sodium feldspar to produce zircon frit with high strength, high whiteness, high toughness, and the ability to promote low-temperature sintering. When zircon frit is added to ceramic blanks, it helps to improve the relevant properties of the ceramic blanks.

[0044] Secondly, the raw materials for the ceramic blanks in this technical solution also include lithium tailings, which contain potassium oxide and sodium oxide, which have a fluxing effect. The lithium tailings account for 50-70 parts, and the use of a large amount of lithium tailings is beneficial to significantly reducing the calcination temperature and calcination time of the ceramic blanks. In addition, zirconium frit also helps to promote low-temperature rapid sintering. Through the combination of the two, the calcination temperature of the ceramic blanks is reduced to 1100-1140℃, and the calcination time is reduced to 35-40 minutes. Compared with the existing calcination temperature of around 1200℃ and calcination time of 60-90 minutes for ceramic blanks, this technical solution greatly shortens the calcination temperature and calcination time, achieving low-cost and green production, which is conducive to improving the competitiveness of ceramic products.

[0045] Although lithium tailings can help significantly reduce calcination temperature and time, the large-scale use of lithium tailings can easily lead to a significant reduction in the strength of ceramic green bodies due to the inherent limitations of lithium tailings. Therefore, this technical solution further optimizes the ceramic green body formulation.

[0046] Specifically, the raw materials for the ceramic body in this technical solution also include clay, whose chemical composition is mainly silicon dioxide and aluminum oxide. Since the aluminum content of the clay is generally 30-35%, which is relatively high, and higher aluminum content makes the ceramic body easier to form and increases its strength, the clay can improve the strength of the ceramic body. In addition, the mesh size of the clay is generally 200-300 mesh, with fine particles typically within the colloidal size range, giving it excellent physical adsorption and surface chemical activity. This allows the clay to bond tightly with other raw materials during the calcination process, thereby improving the strength of the ceramic body.

[0047] This technical solution utilizes the synergy of zirconium frit and clay to enhance the strength of the ceramic green body. This combination leverages both the strength-enhancing properties of the zirconium frit and the strength-boosting properties of the clay, ensuring and improving the strength of the ceramic green body even with the use of large quantities of lithium tailings and reduced calcination temperature and time. Furthermore, the zirconium frit in this solution possesses high toughness, preventing brittle fracture of the ceramic green body under significant impact or stress, which could lead to a substantial decrease in strength. In addition, the stable chemical composition of the clay, unaffected by external environmental factors, ensures the stability of its properties during calcination, guaranteeing the long-term strength of the ceramic green body. Moreover, the high whiteness of the clay imparts a high whiteness to the ceramic green body, which, combined with the high whiteness of the zirconium frit, further enhances the whiteness of the ceramic green body.

[0048] Furthermore, the large addition of lithium tailings to the formula also means that the content of potassium oxide and sodium oxide in the ceramic body formula is relatively high. Since potassium oxide and sodium oxide have a large coefficient of thermal expansion, the large use of lithium tailings can easily lead to excessive shrinkage during the calcination process of the ceramic body, resulting in cracks in the obtained ceramic body and affecting its structural strength.

[0049] The ceramic green body in this technical solution also includes wollastonite as a raw material. The chemical components of wollastonite, silicon dioxide and calcium oxide, provide a low coefficient of thermal expansion and good thermal shock resistance, thereby reducing the shrinkage rate of the ceramic green body during calcination. Simultaneously, the fine particles of the clay allow it to form a dense packing when mixed with other raw materials, reducing porosity and effectively decreasing the shrinkage rate of the ceramic green body during calcination. Furthermore, zirconium frit helps reduce the coefficient of thermal expansion of the ceramic green body, meaning it helps reduce the shrinkage rate during the ceramic green body process. Through the synergistic effect of wollastonite, clay, and zirconium frit, the shrinkage rate of the ceramic green body during calcination is greatly reduced, thus preventing the obtained ceramic green body from easily cracking and ensuring its strength.

[0050] Finally, due to the fluxing effect of lithium tailings, the large addition of lithium tailings to the formula will significantly reduce the calcination temperature of the ceramic blank. When the calcination temperature of the ceramic blank is too low, the moisture and gas generated during the calcination process cannot be completely removed in time, which can easily make the internal structure of the calcined ceramic blank loose, further leading to a decrease in the strength of the ceramic blank.

[0051] This technical solution utilizes the needle-like crystal structure of wollastonite to provide channels for the release of moisture and gases generated during the calcination of ceramic green bodies. This allows for rapid removal of moisture and gases, preventing the internal structure of the ceramic green body from becoming porous and leading to a decrease in strength. Simultaneously, wollastonite also facilitates rapid preheating and cooling processes, contributing to low-temperature rapid firing. Furthermore, wollastonite exhibits good whiteness, which helps improve the whiteness of the ceramic green body.

[0052] Furthermore, the raw materials for the ceramic body include 25-35 parts of clay, 50-70 parts of lithium tailings, 1-5 parts of wollastonite, and 5-10 parts of zirconium frit. Based on the properties of each raw material in the ceramic body formula, the amount of each raw material added is limited, which helps to ensure the performance of the ceramic body.

[0053] Therefore, this technical solution improves strength and whiteness by combining the raw materials—ceramic clay, lithium tailings, wollastonite, and zirconium frit—in the ceramic body, and by limiting the composition of the raw materials within a certain range of addition amounts, while making extensive use of lithium tailings and reducing the calcination temperature and time of the ceramic body. Furthermore, the combination of clay and composite zirconium in this technical solution helps to improve strength and whiteness at a lower cost.

[0054] Preferably, the raw materials of the ceramic blank, calculated by mass parts, further include 2 to 10 parts of mineralizer, 0.3 to 1 part of desiccant, and 1 to 3 parts of binder.

[0055] In a preferred embodiment of this technical solution, a mineralizer, a degumming agent, and a binder are further included, which can be selected according to actual needs. The mineralizer includes at least one of diopside, talc, magnesia, and fluorite; the degumming agent includes at least one of sodium tripolyphosphate, ammonium hexametaphosphate, and sodium humate; and the binder is selected from at least one of sodium carboxymethyl cellulose, sodium methyl starch, and polyvinyl alcohol.

[0056] To further explain, the raw materials of the zircon frit, calculated by mass, include 25-35 parts alumina, 15-23 parts quartz, 18-22 parts composite zircon, 15-23 parts potassium feldspar, and 8-13 parts sodium feldspar; and the mixing ratio of alumina to quartz is (1.5-2):1.

[0057] In a preferred embodiment of this technical solution, optimizing the proportions of each raw material in the zircon frit formulation helps ensure the performance of the zircon frit at a lower cost. Furthermore, limiting the mixing ratio of quartz and alumina not only facilitates the formation of mullite from quartz and alumina, but also ensures high strength and a low coefficient of expansion for the zircon frit.

[0058] To further clarify, the whiteness of the composite zirconium is ≥60°, the whiteness of the ball soil is ≥65°, and the whiteness of the wollastonite is ≥60°.

[0059] In a preferred embodiment of this technical solution, limiting the whiteness of the composite zirconium and clay helps to improve the whiteness of the ceramic blank, thereby ensuring the whiteness of the ceramic body obtained by firing the ceramic blank, and thus ensuring the decorative effect of the ceramic tile.

[0060] To further clarify, the lithium tailings include the Dafu lithium tailings and the Shimen medium-temperature sand lithium tailings;

[0061] The chemical composition of the Dafu lithium tailings, calculated by mass percentage, includes SiO2 78.69–78.77%, Al2O3 12.43–12.70%, Fe2O3 0.08–0.15%, TiO2 0–0.02%, CaO 0.30–0.60%, MgO 0.06–0.08%, K2O 2.36–2.56%, and Na2O 4.58–4.68%, with the remainder being loss on ignition.

[0062] The chemical composition of the Shimen medium-temperature lithium tailings, calculated by mass percentage, includes SiO2 69.52–69.60%, Al2O3 18.68–18.72%, Fe2O3 0.43–0.53%, TiO2 0.02–0.06%, CaO 0.78–0.10%, MgO 0.15–0.21%, K2O 2.53–2.78%, Na2O 4.12–4.32%, and Li2O 0.24–0.30%, with the remainder being loss on ignition.

[0063] In a preferred embodiment of this technical solution, the lithium tailings include Dafu lithium tailings and Shimen medium-temperature sandy lithium tailings. Both Dafu and Shimen medium-temperature sandy lithium tailings contain sodium oxide and potassium oxide, which helps ensure the fluxing effect of the lithium tailings. In addition, the Shimen medium-temperature sandy lithium tailings also contain lithium oxide, which further enhances the fluxing effect of the lithium tailings.

[0064] Preferably, the chemical composition of the rich lithium tailings, calculated by mass percentage, includes 78.69% SiO2, 12.57% Al2O3, 0.12% Fe2O3, 0.02% TiO2, 0.50% CaO, 0.07% MgO, 2.46% K2O, and 4.63% Na2O, with the remainder being loss on ignition.

[0065] The chemical composition of the Shimen medium-temperature lithium tailings, calculated by mass percentage, includes 69.56% SiO2, 18.70% Al2O3, 0.48% Fe2O3, 0.06% TiO2, 0.88% CaO, 0.21% MgO, 2.72% K2O, 4.22% Na2O, and 0.27% Li2O, with the remainder being loss on ignition.

[0066] To further clarify, the Dafu lithium tailings have a particle size ≤1cm and a whiteness of 50~58°;

[0067] The particle size of the medium-temperature lithium tailings from the Shimen mine is ≤2cm, and the whiteness is 20-25°.

[0068] In a preferred embodiment of this technical solution, limiting the particle size of Dafu lithium tailings and Shimen medium-temperature lithium sand tailings is beneficial for both improving utilization and ensuring fluxing effect. Furthermore, limiting the whiteness of Dafu lithium tailings and Shimen medium-temperature lithium sand tailings also helps ensure the whiteness of the ceramic blank.

[0069] To further explain, based on the mass ratio, the mixing ratio of the Dafu lithium tailings and the Shimen medium-temperature sand lithium tailings is (1-2):1.

[0070] Since the medium-temperature lithium sand tailings of Shimen contain lithium oxide, their fluxing effect is better than that of the rich lithium tailings. However, since the price of the medium-temperature lithium sand tailings of Shimen is higher than that of the rich lithium tailings, in a preferred embodiment of this technical solution, the mixing ratio of the rich lithium tailings and the medium-temperature lithium sand tailings of Shimen is limited to (1~2):1. This is beneficial to improve the fluxing effect of the lithium tailings at a lower cost, thereby promoting the low-temperature rapid sintering of the ceramic blank.

[0071] A method for preparing ceramic bricks, using the aforementioned lithium tailings-based ceramic blank, includes the following steps:

[0072] A. Mix the alumina, quartz, composite zircon, potassium feldspar and sodium feldspar in the specified amounts evenly, calcine and quench in water to obtain zircon frit;

[0073] B. Mix the formula-formulated clay, lithium tailings, wollastonite and zirconium frit evenly to obtain a lithium tailings-based ceramic blank;

[0074] C. The blank is rolled into a ceramic blank and dried to obtain a ceramic body.

[0075] D. The ceramic bricks are calcined in a kiln and then polished to obtain ceramic bricks; wherein the calcination temperature is 1100-1140℃ and the calcination time is 35-40min.

[0076] This technical solution also proposes a method for preparing ceramic tiles. The method is simple and easy to operate, which solves the problem that the large-scale use of lithium tailings in the prior art leads to a decrease in the strength of ceramic tiles. At the same time, it improves the whiteness of ceramic tiles and ensures the decorative effect of ceramic tiles.

[0077] Furthermore, the calcination temperature is 1100–1140℃ and the calcination time is 35–40 min. Based on the properties of the ceramic blank, ceramic bricks can be obtained even at a lower calcination temperature and shorter calcination time, achieving low-cost and green production, which is conducive to improving the competitiveness of ceramic products.

[0078] It should be noted that this technical solution also includes steps E and F, with step E following step C. The specific steps of step E are: printing color ink according to a preset pattern to form a color pattern layer.

[0079] Step F follows step E. Specifically, step F involves applying a digital protective glaze to form a protective glaze layer.

[0080] It should be further noted that the inkjet printing layer in this technical solution uses conventional colored inks from the ceramics industry, and the colored inks will not be described further here. The glaze applied to the protective glaze layer is a conventional glaze from the ceramics industry, and the protective glaze will not be described further here. In addition, the protective glaze can be applied by spraying or dipping, and there is no limitation here.

[0081] To further explain, in step C, the drying temperature is 170–190°C, and the drying time is 30–60 min.

[0082] In a preferred embodiment of this technical solution, the drying time and temperature of the ceramic body are optimized to ensure that the ceramic body is completely dried. If the drying temperature is too high or the drying time is too long, it will not be very effective in reducing prickly heat blisters; if the drying temperature is too low or the drying time is too short, it will increase the moisture content of the ceramic body, reduce the strength of the ceramic body, and affect the loss.

[0083] To further explain, in step A, the firing curve of the zirconium ingot is as follows:

[0084] (1) It takes 1 to 3 hours to heat the temperature from room temperature to 500℃;

[0085] (2) The temperature rises from 500℃ to 1100℃ in 0.5 to 1.5 hours;

[0086] (3) The temperature rises from 1100℃ to 1500℃ in 0.5 to 1.5 hours;

[0087] (4) 1500℃, keep warm for 0.5~1h.

[0088] In one embodiment of this technical solution, the firing curve of the zirconium frit includes three heating processes and one holding process. During the heating process from room temperature to 500°C, moisture, gaseous oxides, and volatile substances in the zirconium frit raw material will volatilize under high temperature conditions. Subsequently, the heating process from 500°C to 1100°C begins. During this heating process, alumina in the zirconium frit raw material and silica in quartz react to form the main crystalline phase mullite. Then, during the heating process from 1100°C to 1500°C, zirconium oxide in the composite zirconium transforms from a monoclinic crystalline phase to a more ductile cubic crystalline phase, thereby ensuring a significant improvement in the toughness and strength of the zirconium frit. Finally, the temperature is held at 1500°C to maintain the cubic crystalline state of the zirconium oxide in the composite zirconium, thereby improving toughness.

[0089] A ceramic tile, prepared using the above-described method for preparing ceramic tiles, wherein the ceramic tile has a modulus of rupture ≥32MPa and a breaking strength ≥2000N.

[0090] This technical solution also proposes a ceramic tile with a rupture modulus ≥32MPa and a breaking strength ≥2000N, which has high strength while ensuring the decorative effect of the ceramic tile.

[0091] The technical solution of the present invention will be further illustrated below through specific embodiments.

[0092] Example group

[0093] Example 1

[0094] A method for preparing ceramic bricks using lithium tailings-based ceramic blanks includes the following steps:

[0095] A. Mix 30 parts of alumina, 20 parts of quartz, 20 parts of composite zirconium, 20 parts of potassium feldspar and 10 parts of sodium feldspar evenly, calcine and quench in water to obtain zirconium frit; wherein, the whiteness of the composite zirconium is 65°, the manufacturer of the composite zirconium is Yifeng Huaqiang Inorganic Materials Co., Ltd., and the model is composite zirconium 50.

[0096] B. A ceramic blank based on lithium tailings was prepared by uniformly mixing 30 parts of spherical clay, 60 parts of lithium tailings (made from Dafu lithium tailings and Shimen medium-temperature sand lithium tailings in a 1:1 ratio), 5 parts of wollastonite, and 5 parts of zircon frit. The spherical clay had a whiteness of 80°; the wollastonite had a needle-like crystal structure and a whiteness of 60°; the Dafu lithium tailings had a particle size of 0.5 cm and a whiteness of 55°. The chemical composition of the Dafu lithium tailings, calculated by mass percentage, included 78.69% SiO2, 12.57% Al2O3, 0.12% Fe2O3, 0.02% TiO2, 0.50% CaO, 0.07% MgO, and K2O. The chemical composition of the Shimen medium-temperature sand-lithium tailings, calculated by mass percentage, includes 69.56% SiO2, 18.70% Al2O3, 0.48% Fe2O3, 0.06% TiO2, 0.88% CaO, 0.21% MgO, 2.72% K2O, 4.22% Na2O, and 0.27% Li2O, with the remainder being loss on ignition. The particle size of the Shimen medium-temperature sand-lithium tailings is 1.8 cm, and the whiteness is 22°.

[0097] C. The blank is rolled into a ceramic blank by roller pressing, and then dried at 180℃ for 45 minutes to obtain a ceramic body;

[0098] D. After being calcined in the kiln at 1100℃ for 40 minutes, the ceramic bricks are obtained after polishing.

[0099] Example 2

[0100] A method for preparing ceramic bricks using lithium tailings-based ceramic blanks includes the following steps:

[0101] A. Mix 26 parts of alumina, 16 parts of quartz, 22 parts of composite zirconium, 23 parts of potassium feldspar and 13 parts of sodium feldspar evenly, calcine and quench in water to obtain zirconium frit; wherein, the whiteness of the composite zirconium is 65°, the manufacturer of the composite zirconium is Yifeng Huaqiang Inorganic Materials Co., Ltd., and the model is composite zirconium 50.

[0102] B. A ceramic blank based on lithium tailings was prepared by uniformly mixing 25 parts of ball soil, 70 parts of lithium tailings (combined with Dafu lithium tailings and Shimen medium-temperature sand lithium tailings at a ratio of 1.5:1), 2 parts of wollastonite, and 8 parts of zircon frit. The ball soil had a whiteness of 80°; the wollastonite had a needle-like crystal structure and a whiteness of 65°; the Dafu lithium tailings had a particle size of 0.8 cm and a whiteness of 58°. The chemical composition of the Dafu lithium tailings, calculated by mass percentage, included 78.69% SiO2, 12.57% Al2O3, 0.12% Fe2O3, 0.02% TiO2, 0.50% CaO, 0.07% MgO, and K2O. The chemical composition of the Shimen medium-temperature sand-lithium tailings, calculated by mass percentage, includes SiO2 69.56%, Al2O3 18.70%, Fe2O3 0.48%, TiO2 0.06%, CaO 0.88%, MgO 0.21%, K2O 2.72%, Na2O 4.22%, and Li2O 0.27%, with the remainder being loss on ignition. The particle size of the Shimen medium-temperature sand-lithium tailings is 1.2 cm, and the whiteness is 25°.

[0103] C. The blank is pressed into a ceramic blank by roller pressing, and then dried at 170℃ for 60 minutes to obtain a ceramic body;

[0104] D. After being calcined in the kiln at 1140℃ for 35 minutes, the ceramic bricks are obtained after polishing.

[0105] Example 3

[0106] A method for preparing ceramic bricks using lithium tailings-based ceramic blanks includes the following steps:

[0107] A. Mix 35 parts of alumina, 23 parts of quartz, 18 parts of composite zirconium, 15 parts of potassium feldspar and 9 parts of sodium feldspar evenly, calcine and quench in water to obtain zirconium frit; wherein, the whiteness of the composite zirconium is 65°, the manufacturer of the composite zirconium is Yifeng Huaqiang Inorganic Materials Co., Ltd., and the model is composite zirconium 50.

[0108] B. A ceramic blank based on lithium tailings was prepared by uniformly mixing 25 parts of ball soil, 50 parts of lithium tailings (combined with Dafu lithium tailings and Shimen medium-temperature sand lithium tailings in a 2:1 ratio), 1 part of wollastonite, and 10 parts of zirconium frit. The ball soil had a whiteness of 80°; the wollastonite had a needle-like crystal structure and a whiteness of 62°; the Dafu lithium tailings had a particle size of 1 cm and a whiteness of 50°. The chemical composition of the Dafu lithium tailings, calculated by mass percentage, included 78.69% SiO2, 12.57% Al2O3, 0.12% Fe2O3, 0.02% TiO2, 0.50% CaO, 0.07% MgO, and K2O. The chemical composition of the Shimen medium-temperature sand-lithium tailings, calculated by mass percentage, includes 69.56% SiO2, 18.70% Al2O3, 0.48% Fe2O3, 0.06% TiO2, 0.88% CaO, 0.21% MgO, 2.72% K2O, 4.22% Na2O, and 0.27% Li2O, with the remainder being loss on ignition. The particle size of the Shimen medium-temperature sand-lithium tailings is 1.5 cm, and the whiteness is 25°.

[0109] C. The blank is rolled into a ceramic blank by roller pressing, and then dried at 190℃ for 30 minutes to obtain a ceramic body;

[0110] D. After being calcined in the kiln at 1120℃ for 38 minutes, the ceramic bricks are obtained after polishing.

[0111] Comparative group

[0112] Comparative Example 1

[0113] The preparation method and raw materials of Comparative Example 1 are the same as those of Example 1, except that zirconium frit is not added to the ceramic blank formulation of Comparative Example 1.

[0114] Comparative Example 2

[0115] Comparative Example 2 uses the same preparation method and raw materials as Example 1, except that wollastonite is not added to the ceramic blank formulation in Comparative Example 2.

[0116] Comparative Example 3

[0117] The preparation method and raw materials of Comparative Example 3 are the same as those of Example 1, except that lithium tailings are not added to the ceramic blank formulation of Comparative Example 3.

[0118] Comparative Example 4

[0119] The preparation method and raw materials of Comparative Example 4 are the same as those of Example 1, except that composite zirconium is not added to the ceramic blank formulation of Comparative Example 4.

[0120] Ceramic tiles were prepared using different preparation methods described in the above embodiments and comparative examples. The surface decoration effects of the ceramic tiles prepared using different preparation methods described in the above embodiments and comparative examples were observed. The strength of the obtained ceramic tiles was tested using the test method of GB / T3810.7-2016 "Ceramic Tiles Test Methods Part 4: Determination of Modulus of Fracture and Breaking Strength". The test results are shown in Table 1 below.

[0121] Table 1. Performance test results of different ceramic tiles in the examples and comparative examples.

[0122]

[0123]

[0124] As can be seen from the performance test results of each embodiment in the table above, the ceramic tile prepared by a certain method has a rupture modulus ≥32MPa and a breaking strength ≥2000N, which not only ensures the decorative effect of the ceramic tile, but also has high strength.

[0125] In Comparative Example 1, the absence of zirconium frit resulted in decreased strength and whiteness of the ceramic body, thus affecting the strength and decorative effect of the ceramic tile. Furthermore, the lack of zirconium frit also easily led to incomplete firing of the ceramic tile, resulting in a significant decrease in the strength of the final product and an uneven glaze, thereby impacting the decorative effect of the ceramic tile.

[0126] In Comparative Example 2, the absence of wollastonite prevented the timely release of gases and moisture generated during the firing process of the ceramic body, resulting in decreased strength of the ceramic body and consequently, weaker ceramic tiles. Furthermore, the lack of wollastonite also negatively impacted the whiteness of the ceramic body, thus affecting the decorative effect of the ceramic tiles.

[0127] In Comparative Example 3, the ceramic blank could not be fully calcined due to the lack of lithium tailings, resulting in a significant decrease in the strength of the product and an uneven glaze, which affected the decorative effect.

[0128] In Comparative Example 4, the absence of composite zirconium in the zirconium frit reduced the strength, toughness, and whiteness of the zirconium frit, resulting in a decrease in the strength and decorative effect of the final ceramic tile.

[0129] The technical principles of the present invention have been described above with reference to specific embodiments. These descriptions are merely for explaining the principles of the invention and should not be construed as limiting the scope of protection of the invention in any way. Based on this explanation, those skilled in the art can readily conceive of other specific embodiments of the invention without inventive effort, and these embodiments will all fall within the scope of protection of the present invention.

Claims

1. A ceramic blank based on lithium tailings, characterized in that: According to the mass fractions, the raw materials of the ceramic blank include 25-35 parts of clay, 50-70 parts of lithium tailings, 1-5 parts of wollastonite, and 5-10 parts of zirconium frit; wherein, the chemical composition of the lithium tailings includes potassium oxide and sodium oxide; and the crystal structure of the wollastonite is a needle-like crystal structure. The raw materials of the zircon frit, calculated by mass, include 25-35 parts alumina, 15-23 parts quartz, 18-22 parts composite zircon, 15-23 parts potassium feldspar, and 8-13 parts sodium feldspar; and the mixing ratio of alumina to quartz is (1.5-2):

1. The composite zirconium is composed of alumina and zirconium oxide.

2. The ceramic blank based on lithium tailings according to claim 1, characterized in that: The whiteness of the composite zirconium is ≥60°, the whiteness of the ball soil is ≥65°, and the whiteness of the wollastonite is ≥60°.

3. The ceramic blank based on lithium tailings according to claim 1, characterized in that: The lithium tailings include Dafu lithium tailings and Shimen medium-temperature sand lithium tailings. The chemical composition of the Dafu lithium tailings, calculated by mass percentage, includes SiO2 78.69–78.77%, Al2O3 12.43–12.70%, Fe2O3 0.08–0.15%, TiO2 0–0.02%, CaO 0.30–0.60%, MgO 0.06–0.08%, K2O 2.36–2.56%, and Na2O 4.58–4.68%, with the remainder being loss on ignition. The chemical composition of the Shimen medium-temperature lithium tailings, calculated by mass percentage, includes SiO2 69.52–69.60%, Al2O3 18.68–18.72%, Fe2O3 0.43–0.53%, TiO2 0.02–0.06%, CaO 0.78–0.10%, MgO 0.15–0.21%, K2O 2.53–2.78%, Na2O 4.12–4.32%, and Li2O 0.24–0.30%, with the remainder being loss on ignition.

4. A ceramic blank based on lithium tailings according to claim 3, characterized in that: The Dafu lithium tailings have a particle size of ≤1cm and a whiteness of 50-58°. The particle size of the medium-temperature lithium tailings from the Shimen mine is ≤2cm, and the whiteness is 20-25°.

5. A ceramic blank based on lithium tailings according to claim 3, characterized in that: Based on the mass ratio, the mixing ratio of the Dafu lithium tailings and the Shimen medium-temperature sand lithium tailings is (1-2):

1.

6. A method for preparing ceramic bricks, characterized in that: Using the lithium tailings-based ceramic blank according to any one of claims 1 to 5, the process includes the following steps: A. Mix the alumina, quartz, composite zircon, potassium feldspar and sodium feldspar in the specified amounts evenly, calcine and quench in water to obtain zircon frit; B. Mix the formula-formulated clay, lithium tailings, wollastonite and zirconium frit evenly to obtain a lithium tailings-based ceramic blank; C. The blank is rolled into a ceramic blank and dried to obtain a ceramic body. D. The ceramic bricks are calcined in a kiln and then polished to obtain ceramic bricks; wherein the calcination temperature is 1100-1140℃ and the calcination time is 35-40min.

7. The method for preparing a ceramic brick according to claim 6, characterized in that: In step C, the drying temperature is 170–190°C, and the drying time is 30–60 min.

8. The method for preparing a ceramic brick according to claim 6, characterized in that: In step A, the firing curve of the zirconium ingot is as follows: (1) It takes 1 to 3 hours to heat the temperature from room temperature to 500℃; (2) The temperature rises from 500℃ to 1100℃ in 0.5 to 1.5 hours; (3) The temperature rises from 1100℃ to 1500℃ in 0.5 to 1.5 hours; (4) 1500℃, keep warm for 0.5 to 1 hour.

9. A ceramic tile, characterized in that: The ceramic brick is prepared using the method described in any one of claims 6 to 8, wherein the modulus of rupture is ≥32MPa and the breaking strength is ≥2000N.

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