A low-temperature fast-firing ceramic body, high-strength ceramic brick and preparation method thereof

Abstract

The present invention provides a low-temperature fast-firing ceramic body, a high-strength ceramic brick and a preparation method thereof. The raw materials of the ceramic body include, by weight, 8 to 15 parts of ball clay, 1 to 8 parts of bentonite, 1 to 8 parts of black talc, 60 to 70 parts of vanadium-titanium slag, 8 to 15 parts of kaolin, and 0.3 to 0.5 parts of a body disintegrator. The present invention introduces a large amount of vanadium-titanium slag into the ceramic body formula, which can completely replace the barren raw materials in the blank, slow down the depletion of mineral resources, greatly improve the utilization rate of vanadium-titanium slag, avoid resource waste, and form a low-aluminum body formula system enhanced with metal oxides, which can greatly reduce the sintering temperature of the body, reduce the water absorption rate of the product, shorten the firing cycle, and realize a low-temperature fast-firing ceramic production process.

Description

Technical Field

[0001] The invention relates to the technical field of ceramics, and in particular to a low-temperature fast-firing ceramic body, a high-strength ceramic brick and a preparation method thereof. Background Art

[0002] With the rapid development of economy and construction industry, people's living standard is improving, and the ceramic industry has developed rapidly. However, due to the excessive exploitation and unreasonable use of mineral resources in the ceramic industry, high-quality ceramic raw materials are becoming less and less, which directly or indirectly affects the sustainable development of the ceramic industry itself. How to use low-quality raw materials to produce high-quality ceramic tiles has become an urgent problem that the industry needs to solve.

[0003] On the other hand, ironmaking will discharge a large amount of vanadium-titanium slag. According to relevant data, every ton of iron smelting can produce about 0.3 to 1 ton of waste slag. The lower the ore grade, the greater the slag discharge. Due to the high vanadium-titanium slag content, it cannot be directly used to produce slag silicate cement; and because its titanium grade is not high enough, it cannot be used as a raw material for the titanium industry. Therefore, a large amount of vanadium-titanium slag cannot be reasonably utilized, which not only causes a waste of resources, occupies a huge area of ​​the yard, but also pollutes the environment.

[0004] Therefore, the prior art has defects and needs to be improved and developed. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a low-temperature fast-fired ceramic body, a high-strength ceramic brick and a preparation method thereof in view of the above-mentioned defects of the prior art, aiming to solve the problem that vanadium-titanium slag is not reasonably utilized in the prior art.

[0006] The technical solution adopted by the present invention to solve the technical problem is as follows:

[0007] The first aspect of the present application provides a low-temperature fast-firing ceramic body, wherein the raw materials of the ceramic body include, by weight:

[0008] 8-15 parts of ball clay, 1-8 parts of bentonite, 1-8 parts of black talc, 60-70 parts of vanadium-titanium slag, 8-15 parts of kaolin, and 0.3-0.5 parts of green body debonding agent.

[0009] Optionally, in one embodiment of the present application, the chemical components of the ceramic body include, by weight:

[0010] SiO2 25-35 parts, Al2O3 5-10 parts, K2O 0.2-1.5 parts, Na2O 1-4.5 parts, CaO 1.0-2.5 parts, MgO 1.5-3.5 parts, TiO2 7.5-11.45 parts, Fe2O3 25.5-35.5 parts, Cr2O3 2.5-3.5 parts, MnO 4.5-6.9 parts.

[0011] Optionally, in one embodiment of the present application, the chemical components of the vanadium-titanium slag include, by weight percentage:

[0012] Loss on ignition 1.16~1.55%, Al2O3 3.5~4.56%, SiO2 12.55~18.05%, Fe2O342.65~49.47%, CaO 2.05~3.71%, MgO 2.5~3.55%, K2O 0.01~0.05%, Na2O3.55~5.91%, TiO2 8.95~12.25%, MnO 7.85~11.58%, Cr2O3 2.35~5.51%.

[0013] The present invention also provides a high-strength ceramic tile, comprising: the ceramic body as described above, a base glaze layer arranged on the ceramic body, a pattern decoration layer arranged on the base glaze layer, and a surface glaze layer arranged on the pattern decoration layer.

[0014] Optionally, in one embodiment of the present application, the raw materials of the base glaze layer include, by weight:

[0015] 5-10 parts of kaolin, 10-15 parts of quartz, 50-60 parts of albite, 10-15 parts of potassium feldspar, 1-5 parts of calcined talc, 0-5 parts of zirconium silicate, 2-8 parts of calcite, 0.3-0.5 parts of sodium tripolyphosphate, and 0.1-0.2 parts of carboxymethyl cellulose.

[0016] Optionally, in one embodiment of the present application, the chemical components of the base glaze layer include, by weight percentage:

[0017] SiO2 55~60%, Al2O3 15~25%, Na2O 5~8%, K2O 1.5~2.5%, CaO 1~5%, MgO0.5~1.5%, ZrO2 0.1~0.5%, Fe2O3 0.15~0.3%.

[0018] Optionally, in one embodiment of the present application, the raw materials of the glaze layer include, by weight:

[0019] 20-30 parts of frit, 5-12 parts of kaolin, 1-3 parts of calcined kaolin, 5-10 parts of quartz, 2-8 parts of barium carbonate, 25-38 parts of albite, 5-8 parts of calcite, 3-9 parts of calcined talc, 3-5 parts of zinc oxide, 0.3-0.5 parts of sodium tripolyphosphate, and 0.1-0.2 parts of carboxymethyl cellulose.

[0020] Optionally, in one embodiment of the present application, the chemical components of the frit include, by weight percentage:

[0021] SiO2 45.5~55.72%, Al2O3 5.0~10.5%, K2O 0.35~3.25%, Na2O3.85~8.45%, CaO 7.5~12.5%, MgO 0.59~3.85%, Fe2O3 0.1~0.25%, B2O32.5~5.55%, BaO 7.5~12.55%, ZnO 10.55~15.52%.

[0022] Optionally, in one embodiment of the present application, the chemical components of the glaze layer include, by weight percentage:

[0023] SiO2 45.5~58.89%, Al2O3 10.5~15.8%, K2O 1.05~1.82%, Na2O3.5~5.44%, CaO 5.5~8.85%, MgO 0.5~3.84%, Fe2O3 0.1~0.36%, B2O30.1~3.25%, BaO 5.5~8.67%, ZnO 4.35~6.72%.

[0024] The present invention also provides a method for preparing the high-strength ceramic brick as described above, comprising:

[0025] The raw materials are mixed and ground according to the formula ratio to obtain a formula slurry that meets the preset fineness, and the formula slurry is sieved, aged, and impurities are removed, and then spray-dried to obtain a powder;

[0026] The powder is pressed into a shape, dried in a drying kiln to obtain a ceramic body, and a base glaze is applied on the ceramic body to obtain a base glaze layer;

[0027] Performing inkjet decoration on the base glaze layer to obtain a pattern decoration layer, applying a top glaze on the pattern decoration layer to obtain the top glaze layer and then drying to obtain a glaze blank;

[0028] The glaze blank is fired at a firing temperature of 1060° C. to 1100° C. and a firing period of 35 to 60 minutes to obtain a high-strength ceramic tile.

[0029] The present invention discloses a low-temperature fast-firing ceramic body, a high-strength ceramic brick and a preparation method thereof. The raw materials of the ceramic body include, by weight, 8 to 15 parts of ball clay, 1 to 8 parts of bentonite, 1 to 8 parts of black talc, 60 to 70 parts of vanadium-titanium slag, 8 to 15 parts of kaolin, and 0.3 to 0.5 parts of a body disintegrator. The present invention introduces a large amount of vanadium-titanium slag into the formula of the ceramic body, which can completely replace the barren raw materials in the blank, slow down the depletion of mineral resources, greatly improve the utilization rate of vanadium-titanium slag, avoid waste of resources, and form a low-aluminum body formula system enhanced with metal oxides, which can greatly reduce the sintering temperature of the body, reduce the water absorption rate of the product, shorten the firing cycle, and realize a low-temperature fast-firing ceramic production process. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 It is a flow chart of a preferred embodiment of a method for preparing high-strength ceramic bricks in the present invention.

[0031] Figure 2 It is a specific production process flow chart for preparing high-strength ceramic bricks in the present invention. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical solution and advantages of the present invention clearer and more specific, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0033] The invention provides a low-temperature fast-firing ceramic body. The raw materials of the ceramic body include, by weight, 8 to 15 parts of ball clay, 1 to 8 parts of bentonite, 1 to 8 parts of black talc, 60 to 70 parts of vanadium-titanium slag, 8 to 15 parts of kaolin, and 0.3 to 0.5 parts of a body degumming agent.

[0034] Specifically, by analyzing the composition of vanadium-titanium slag, it can be known that vanadium-titanium slag mainly contains rich metal oxides such as Fe2O3, Cr2O3, MnO, TiO2, and also contains common low-temperature flux components such as CaO, MgO, Na2O, etc. required for the ceramic body formula. The iron oxide in vanadium-titanium slag can be used as a low-temperature flux, and can also be combined with manganese and chromium to become a colorant that makes the body appear black. It can also be combined with other metal oxides in vanadium-titanium slag and SiO2 and Al2O3 in traditional ceramic raw materials to form an isomorphous mixed spinel system, which is beneficial to improve the strength of ceramic products. Therefore, it can be used in large quantities in the field of building materials and ceramics.

[0035] The green body disintegrator may include one or more of sodium tripolyphosphate, sodium pentametaphosphate, sodium humate and water glass.

[0036] The embodiment of the present application uses vanadium-titanium slag as the main raw material of the formula, and the stability requirements of the raw materials are very high. It needs to be repeatedly homogenized and multi-point sampling for component analysis. It can be applied to the blank formula production after meeting the standards. The design of the formula is to use the low-temperature flux Na2O, MgO, CaO components contained in the vanadium-titanium slag itself, and other metal oxides Fe2O3, Cr2O3, MnO, TiO2 contained in it to combine black talc, clay and auxiliary materials to form a blank formula system. By adjusting the SiO2 / Al2O3 molar ratio and the proportion of flux and metal oxide components in the formula, a black blank formula with a short firing cycle, a wide firing range, easy control of kiln firing, and high strength is obtained.

[0037] Furthermore, the raw materials of the ceramic body include, by weight: 10 parts of ball clay, 5 parts of bentonite, 4.6 parts of black talc, 70 parts of vanadium-titanium slag, 10 parts of kaolin, 0.3 parts of sodium tripolyphosphate, and 0.1 parts of carboxymethyl cellulose (CMC).

[0038] In one embodiment of the present application, the chemical components of the ceramic body include, by weight:

[0039] SiO2 25-35 parts, Al2O3 5-10 parts, K2O 0.2-1.5 parts, Na2O 1-4.5 parts, CaO 1.0-2.5 parts, MgO 1.5-3.5 parts, TiO2 7.5-11.45 parts, Fe2O3 25.5-35.5 parts, Cr2O3 2.5-3.5 parts, MnO 4.5-6.9 parts.

[0040] Specifically, the Na2O, CaO, MgO, Fe2O3, Cr2O3, MnO, and TiO2 contained in the vanadium-titanium slag in the ceramic formula raw material of the present invention are combined with clay to form a low-temperature fast-fired blank system during the firing process. Na2O, CaO, and MgO are commonly used low-temperature fluxing agent components in traditional ceramic blank formulas. The present invention combines metal oxides such as TiO2, MnO, and Fe2O3 in the vanadium-titanium blast furnace slag with SiO2, Al2O3, etc. in the clay to form a complex spinel compound and a mullite crystal phase at a temperature of 1060°C to 1100°C, which is beneficial to improving the product strength of the black blank.

[0041] In one embodiment of the present application, the chemical components of the vanadium-titanium slag include, by weight percentage:

[0042] Loss on ignition 1.16~1.55%, Al2O3 3.5~4.56%, SiO2 12.55~18.05%, Fe2O342.65~49.47%, CaO 2.05~3.71%, MgO 2.5~3.55%, K2O 0.01~0.05%, Na2O3.55~5.91%, TiO2 8.95~12.25%, MnO 7.85~11.58%, Cr2O3 2.35~5.51%.

[0043] Specifically, MnO and Fe2O3 are both good fluxing agents and the main coloring agents for black blanks, which can greatly reduce the firing temperature of the blank. Among them, compared with commonly used oxides, MnO is characterized by its excellent infrared radiation function, which makes it more conducive to the overall melting of the melt, and to a certain extent expands the firing range of the ceramic formula. It also has a lower melting point than commonly used oxides. After being combined with Fe2O3, CaO, MgO, and Na2O components, the melting point will become even lower, which has a good fluxing effect. In terms of color development, under oxidizing atmosphere conditions, at 1000°C, SiO2, Al2O3 in the ceramic raw materials and MnO, Fe2O 3、 The reaction of Cr2O3 to form a composite coloring of isomorphous mixed spinel colorants is the main factor for the body to appear black, which can present a relatively pure black or a bluish black tone. In terms of strengthening, the glass melt is formed by the mixed flux of alkaline oxides and other metal oxides in the raw materials, so that part of SiO2 and Al2O3 in the formula reacts in advance, promoting the growth of mullite, and the other part of SiO2 and Al2O3 reacts with metal oxides to form a composite spinel system, which increases the types of crystal phases in the product, increases the content of crystal phases, and reduces the glass phase, greatly improving the strength of ceramic products.

[0044] In this way, the embodiment of the present application not only reduces the harm to the environment caused by the stacking of vanadium-titanium slag, but also the recycling of vanadium-titanium slag makes more reasonable use of mineral resources; it has a low-temperature, fast-burning, high-vanadium-titanium slag formula system, and the vanadium-titanium slag blending ratio in the black blank formula can be as high as 70%, which can replace all potassium, sodium feldspar and part of the flux raw materials in the traditional blank formula; it changes the traditional formula high-aluminum reinforced blank formula system, and establishes a low-aluminum blank formula system reinforced with metal oxides, and the other performances of its products meet the national standards for traditional ceramic products.

[0045] The present invention also provides a high-strength ceramic tile, comprising: the ceramic body as described above, a base glaze layer arranged on the ceramic body, a pattern decoration layer arranged on the base glaze layer, and a surface glaze layer arranged on the pattern decoration layer.

[0046] Specifically, the high-strength ceramic bricks made from the above-mentioned ceramic blanks have a firing temperature range of 1060°C to 1100°C, which greatly reduces the firing temperature of ceramic products and shortens the firing cycle, due to the use of the low-temperature flux contained in the vanadium-titanium slag itself and the reasonable combination of raw materials for the ceramic blanks. Since the formula of the ceramic blank uses the rich metal oxides contained in the vanadium-titanium slag, combined with quartz and alumina in the ceramic formula, a high-strength ceramic formula system is jointly constructed, so that the maximum rupture modulus of the high-strength ceramic bricks can reach 75MPa, while the rupture modulus of traditional ceramic products is 45MPa, which greatly improves the rupture modulus index of ceramic products.

[0047] In one embodiment of the present application, the raw materials of the base glaze layer include, by weight: 5 to 10 parts of kaolin, 10 to 15 parts of quartz, 50 to 60 parts of albite, 10 to 15 parts of potassium feldspar, 1 to 5 parts of calcite, 0 to 5 parts of zirconium silicate, 2 to 8 parts of calcite, 0.3 to 0.5 parts of sodium tripolyphosphate, and 0.1 to 0.2 parts of carboxymethyl cellulose.

[0048] Specifically, since the body formula of the present application is mainly composed of iron oxide combined with Na2O, CaO, and MgO to form a multi-element low-temperature flux, the body formula has a low firing temperature. In order to avoid high-temperature exhaust affecting the body-glaze bonding and glaze quality, the present application has developed a low-temperature base glaze formula that matches it.

[0049] In the embodiment of the present application, the chemical components of the base glaze layer, calculated by weight percentage, include: SiO2 55-60%, Al2O3 15-25%, Na2O 5-8%, K2O 1.5-2.5%, CaO 1-5%, MgO 0.5-1.5%, ZrO2 0.1-0.5%, and Fe2O3 0.15-0.3%.

[0050] Specifically, the specific gravity of the base glaze is controlled to be 1.65-1.70g / mL, the glaze amount (300×300mm specification plate) is 35-40g, the glaze slurry fineness is controlled to be 0.6-1.2% (325 mesh sieve residue), and the glossiness after calcination is not greater than 8°. The large glaze amount and high high-temperature viscosity of the base glaze can minimize the escape of gases decomposed from the green body during the sintering process, resulting in defects such as pinhole melt holes.

[0051] In an embodiment of the present application, the raw materials of the glaze layer include, by weight: 20-30 parts of frit, 5-12 parts of kaolin, 1-3 parts of calcined kaolin, 5-10 parts of quartz, 2-8 parts of barium carbonate, 25-38 parts of albite, 5-8 parts of calcite, 3-9 parts of calcined talc, 3-5 parts of zinc oxide, 0.3-0.5 parts of sodium tripolyphosphate, and 0.1-0.2 parts of carboxymethyl cellulose.

[0052] Specifically, due to the characteristics of the body formula, vanadium-titanium slag will undergo complex decomposition reactions at high temperatures. In order to avoid the high-temperature exhaust affecting the body glaze bonding and glaze quality, a matching low-temperature glaze formula was developed.

[0053] In the embodiment of the present application, the chemical components of the frit include, by weight percentage, SiO2 45.5-55.72%, Al2O3 5.0-10.5%, K2O 0.35-3.25%, Na2O 3.85-8.45%, CaO 7.5-12.5%, MgO 0.59-3.85%, Fe2O3 0.1-0.25%, B2O3 2.5-5.55%, BaO7.5-12.55%, and ZnO 10.55-15.52%.

[0054] In one embodiment of the present application, the chemical components of the frit, measured by weight percentage, include: SiO2 52.17%, Al2O3 5.19%, K2O 0.48%, Na2O 4.85%, CaO 9.02%, MgO 1.82%, Fe2O3 0.12%, B2O3 2.88%, BaO 8.22%, ZnO 14.16%, and ignition loss 1.09%.

[0055] In one embodiment of the present application, the chemical components of the glaze layer, measured by weight percentage, include: SiO2 45.5-58.89%, Al2O3 10.5-15.8%, K2O 1.05-1.82%, Na2O 3.5-5.44%, CaO 5.5-8.85%, MgO 0.5-3.84%, Fe2O3 0.1-0.36%, B2O3 0.1-3.25%, BaO 5.5-8.67%, and ZnO 4.35-6.72%.

[0056] Specifically, the specific gravity of the surface glaze is controlled to be 1.6-1.65 g / mL, the amount of glaze (300×300 mm specification dish) is 20-25 g, and the fineness of the glaze slurry is controlled to be 0.3-0.5% (residue on 325 mesh sieve).

[0057] In one embodiment of the present application, the chemical components of the glaze layer, calculated by weight percentage, include: SiO2 54.52%, Al2O3 14.02%, K2O 1.42%, Na2O 4.44%, CaO 6.85%, MgO 0.84%, Fe2O3 0.16%, B2O3 0.35%, BaO 6.17%, ZnO 5.42%, and ignition loss 5.81%.

[0058] The present invention also provides a method for preparing the high-strength ceramic brick as described above, Figure 1As shown, the preparation method of the high-strength ceramic brick comprises:

[0059] Step S100, mixing and grinding the raw materials according to the formula ratio to obtain a formula slurry meeting a preset fineness, sieving, aging, removing impurities from the formula slurry, and spray drying to obtain a powder;

[0060] Step S200, pressing the powder into a shape, drying it in a drying kiln to obtain a ceramic body, and applying a base glaze on the ceramic body to obtain a base glaze layer;

[0061] Step S300, inkjet decoration is performed on the base glaze layer to obtain a pattern decoration layer, and a top glaze is applied to the pattern decoration layer to obtain the top glaze layer and then dried to obtain a glaze blank;

[0062] Step S400, firing the glaze blank at a firing temperature of 1060°C to 1100°C and a firing period of 35 to 60 minutes to obtain a high-strength ceramic tile.

[0063] like Figure 2 As shown, the vanadium-titanium slag raw material is first processed. Due to the high proportion of vanadium-titanium slag added, the vanadium-titanium slag needs to be homogenized before batching, and multi-point sampling is performed for component analysis and comparison.

[0064] After aging and homogenization, the raw materials in the formula components are fed into the ball mill through the feeder according to the formula ratio to obtain a formula slurry that meets the fineness requirements. Specifically, the raw materials are aged and homogenized, and are hard raw materials. They need to be crushed before batching to improve the efficiency and accuracy of wet ball milling. The raw material coarse crushing fineness is controlled to d50<3mm. When batching, according to the moisture content of each raw material and the percentage of each raw material in the formula design, a belt batcher is used to accurately transport the prepared raw materials into the ball mill.

[0065] The formula slurry is sieved, aged, and impurity-removed, and then spray-dried to obtain a powder, which is then pressed into shape and dried in a drying kiln to obtain a body with a certain strength (1.5MPa to 2.0MPa). Specifically, the raw material is powdered by wet ball milling and spray drying, and then dry-pressed to obtain a ceramic green body. Preferably, the wet ball milling fineness of the ceramic tile green body slurry is controlled to be 1.8% to 2.5% of the 250-mesh screen residue, and the moisture content of the powder is controlled to be 6.5 to 8.0%.

[0066] After drying and having a certain strength, the surface is cleaned, the base glaze is applied, ink is sprayed (decorative patterns), the surface glaze is applied and dried, and the moisture content of the body entering the kiln is controlled to obtain the decorated glaze body. At this point, all the process flows before entering the firing kiln are completed.

[0067] The decorated glaze blanks are sent to the roller kiln for firing at a temperature of 1060℃~1100℃ and a firing cycle of 35~60min to form semi-finished products; the fully polished semi-finished products out of the kiln are subjected to rough polishing, fine polishing, edge grinding, air drying, inspection, color separation, grading and storage to obtain polished tiles with a water absorption rate of less than 0.1%, a rupture modulus of 75MPa, a smooth glaze surface with high transparency, a glossiness of 25~35°, and a Mohs hardness of 3~5 after polishing.

[0068] In this way, the embodiment of the present application solves the problems of severe thixotropy, bulging, pinholes, etc. encountered by the same industry when using vanadium-titanium slag. By processing the lithium slag, the proportion of vanadium-titanium slag in the green body formula is further increased, and its mixing ratio is as high as 70%; the green body formula system reinforced with high aluminum in the traditional formula is changed, and a low aluminum green body formula system reinforced with metal oxides is established. The other properties of the product meet the national standards for traditional ceramic products; 60% to 70% of vanadium-titanium slag is added to the ceramic black body formula, combined with the low-temperature flux contained in it, to form a multi- The billet structure of the combination of low-temperature fluxing agents greatly reduces the firing temperature, shortens the firing time, has a wide firing range and stable product performance; the high-vanadium-titanium slag billet formula utilizes the high iron content of vanadium-titanium slag, combined with a special billet structure design of multiple low-temperature fluxing agents and polycrystalline phase, which greatly improves the fracture modulus of the product; a large amount of vanadium-titanium slag is introduced into the ceramic black billet formula, and a formula structure composed of multiple low-temperature fluxing agents is used to prepare low-temperature fast-firing black billets, which greatly reduces the total energy consumption, increases the service life of kilns and kiln tools, achieves energy conservation and emission reduction, and greatly reduces the cost of ceramic production.

[0069] Specific embodiments are listed below for illustration.

[0070] Embodiment 1

[0071] The blank formulation of this embodiment is as follows according to weight percentage:

[0072] 10 parts of ball clay, 5 parts of bentonite, 4.6 parts of black talc, 70 parts of vanadium-titanium slag, 10 parts of kaolin, 0.3 parts of sodium tripolyphosphate, and 0.1 parts of carboxymethyl cellulose (CMC).

[0073] The chemical composition of the above-mentioned green body formula includes by weight percentage:

[0074] SiO2 30.5%, Al2O3 7.89%, K2O 0.39%, Na2O 3.43%, CaO 1.93%, MgO3.3%, TiO2 8.08%, Fe2O3 31.67%, Cr2O3 3.14%, MnO 6.6%, ignition loss 3.07%.

[0075] This embodiment adopts a low-temperature fast-firing process, with a firing temperature of 1060° C. and a firing time of 35 min. The water absorption rate of the obtained product is 0.06%, and the modulus of rupture of the product is 69 MPa.

[0076] This embodiment includes the following production steps:

[0077] Step A1: The raw materials are aged and homogenized. They are hard raw materials and need to be crushed before batching to improve the efficiency and accuracy of wet ball milling. The coarse crushing fineness of the raw materials is controlled to be d50<3mm;

[0078] Step A2, batching, according to the moisture content of each raw material and the percentage of each raw material in the formula design, use a belt batching machine to accurately convey the prepared raw materials into the ball mill;

[0079] Step A3, the raw materials are powdered by wet ball milling and spray drying process and then dry pressed to obtain ceramic green body. Preferably, the wet ball milling fineness of the ceramic tile green body slurry is controlled to be 1.5% of the residue on a 250-mesh sieve, and the moisture content of the powder is controlled to be 6.8-7.2%;

[0080] Step A4: After the ceramic green body is dried, a base glaze is applied, and after being decorated by a digital inkjet machine, a glaze-on-color green body is formed. Then, a surface glaze is applied on the green body by a glaze-throwing process.

[0081] Due to the characteristics of the formula, vanadium-titanium slag will undergo complex decomposition reactions at high temperatures. In order to avoid the high-temperature exhaust affecting the body-glaze combination and glaze quality, a matching low-temperature base glaze formula was developed. The raw materials of the base glaze include, by weight:

[0082] 8 parts of kaolin, 12 parts of quartz, 55 parts of albite, 14 parts of potassium feldspar, 4 parts of calcined talc, 3 parts of zirconium silicate, 5 parts of calcite, 0.4 parts of sodium tripolyphosphate, and 0.2 parts of carboxymethyl cellulose (CMC).

[0083] The chemical composition of the base glaze, measured by weight percentage, includes:

[0084] SiO2 58.47%, Al2O3 24%, Na2O 8%, K2O 2.4%, CaO 4%, MgO 1.3%, ZrO20.5%, Fe2O3 0.3%, loss on ignition 1.03%.

[0085] The specific gravity of the base glaze is controlled to be 1.65 g / mL, the glaze amount (300×300 mm specification plate) is 38 g, the glaze slurry fineness is controlled to be 0.8% (325 mesh sieve residue), and the glossiness after calcination is not greater than 10°.

[0086] Due to the characteristics of this formula, vanadium-titanium slag will undergo complex decomposition reactions at high temperatures. In order to avoid the high-temperature exhaust gas affecting the body glaze combination and glaze quality, a matching low-temperature glaze formula was developed. The glaze includes the following by weight:

[0087] 26 parts of frit, 10 parts of kaolin, 2 parts of calcined kaolin, 7 parts of quartz, 5 parts of barium carbonate, 33 parts of albite, 6 parts of calcite, 8 parts of calcined talc, 4 parts of zinc oxide; 0.5 parts of sodium tripolyphosphate, and 0.1 parts of carboxymethyl cellulose (CMC).

[0088] The chemical composition of the glaze is composed of the following components by weight percentage:

[0089] SiO2 54.52%, Al2O3 14.02%, K2O 1.42%, Na2O 4.44%, CaO 6.85%, MgO0.84%, Fe2O3 0.16%, B2O3 0.35%, BaO 6.17%, ZnO 5.42%, ignition loss 5.81%.

[0090] The chemical composition of the frit is composed of the following components by weight percentage:

[0091] SiO2 52.17%, Al2O3 5.19%, K2O 0.48%, Na2O 4.85%, CaO 9.02%, MgO 1.82%, Fe2O3 0.12%, B2O3 2.88%, BaO 8.22%, ZnO 14.16%, ignition loss 1.09%.

[0092] The glaze of this embodiment is made of transparent frit, the glaze slurry fineness after processing is 0.3% (325 mesh sieve residue), the glaze slurry specific gravity is controlled to be 1.6g / mL, and the product glazing amount (300×300mm specification plate) is 25g.

[0093] Step A5, after the glaze process is completed, the green body is dried and then put into a roller kiln for firing at a temperature of 1060° C. for 35 minutes to produce a semi-finished product;

[0094] The glaze of this embodiment is sintered at a temperature of 1060° C. to obtain a polished tile with a smooth glaze surface, high transparency, and a glossiness of 35°. The Mohs hardness of the product after polishing reaches 3 to 5.

[0095] Step A6: The semi-finished products of the fully polished type are edge-grinded, air-dried, inspected, color-sorted, graded, and stored.

[0096] Embodiment 2

[0097] The blank formulation of this embodiment is as follows according to weight percentage:

[0098] 10 parts of ball clay, 5 parts of bentonite, 5 parts of black talc, 60 parts of vanadium-titanium slag, 10 parts of kaolin, 9.4 parts of waste porcelain powder, 0.3 parts of sodium tripolyphosphate, and 0.1 parts of carboxymethyl cellulose (CMC).

[0099] The chemical composition of the above green body formula is composed of the following components by weight percentage:

[0100] SiO2 33.55%, Al2O3 9.29%, K2O 0.49%, Na2O 3.23%, CaO 1.71%, MgO 3.3%, TiO2 7.38%, Fe2O3 28.75%, Cr2O3 2.85%, MnO 6.02%, ignition loss 3.43%.

[0101] This embodiment adopts a low-temperature fast-firing process, the firing temperature is 1080° C., and the firing time is 35 minutes; the water absorption rate of the obtained product is 0.04%, and the flexural strength of the product is 75 MPa.

[0102] This embodiment includes the following production steps:

[0103] Step B1, the raw materials are aged and homogenized, and are hard raw materials. They need to be crushed before mixing to improve the efficiency and accuracy of wet ball milling. The coarse crushing fineness of the raw materials is controlled to be d50<3mm;

[0104] Step B2, batching, according to the moisture content of each raw material and the percentage of each raw material in the formula design, use a belt batching machine to accurately convey the prepared raw materials into the ball mill;

[0105] Step B3, the raw materials are powdered by wet ball milling and spray drying process and then dry pressed to obtain ceramic green body. Preferably, the wet ball milling fineness of the ceramic tile green body slurry is controlled to be 1.5% on a 250 mesh sieve, and the moisture content of the powder is controlled to be 6.8-7.2%;

[0106] Step B4: After the ceramic green body is dried, a base glaze is applied, and after being decorated by a digital inkjet machine, a glaze-overcolored green body is formed, and then a surface glaze is applied on the green body by a glaze-throwing process.

[0107] Due to the characteristics of the formula, vanadium-titanium slag will undergo complex decomposition reactions at high temperatures to produce gas. In order to avoid the high-temperature exhaust gas affecting the body glaze combination and glaze quality, a matching low-temperature base glaze formula was developed. The base glaze includes the following by weight:

[0108] 6 parts of kaolin, 14 parts of quartz, 58 parts of albite, 11 parts of potassium feldspar, 2 parts of calcined talc, 1 part of zirconium silicate, 6 parts of calcite, 0.5 parts of sodium tripolyphosphate, and 0.1 parts of carboxymethyl cellulose (CMC).

[0109] The chemical composition of the base glaze is composed of the following components by weight percentage:

[0110] SiO2 59.2%, Al2O3 20%, Na2O 7%, K2O 2.3%, CaO 3%, MgO 1.2%, ZrO2 0.3%, Fe2O3 0.2%, ignition loss 6.8%.

[0111] The specific gravity of the base glaze is controlled to be 1.65 g / mL, the glaze amount (300×300 mm specification plate) is 35 g, the glaze slurry fineness is controlled to be 0.6% (325 mesh sieve residue), and the glossiness after calcination is not greater than 10°.

[0112] Due to the characteristics of the formula, vanadium-titanium slag will undergo complex decomposition reactions at high temperatures. In order to avoid the high-temperature exhaust gas affecting the body glaze combination and glaze quality, a matching low-temperature glaze formula was developed. The glaze includes the following by weight:

[0113] 29 parts of frit, 8 parts of kaolin, 3 parts of calcined kaolin, 10 parts of quartz, 7 parts of barium carbonate, 37 parts of albite, 8 parts of calcite, 4 parts of calcined talc, 3 parts of zinc oxide, 0.3 parts of sodium tripolyphosphate, and 0.2 parts of carboxymethyl cellulose (CMC).

[0114] The chemical composition of the glaze is composed of the following components by weight percentage:

[0115] SiO2 54.52%, Al2O3 14.02%, K2O 1.42%, Na2O 4.44%, CaO 6.85%, MgO0.84%, Fe2O3 0.16%, B2O3 0.35%, BaO 6.17%, ZnO 5.42%, ignition loss 5.81%.

[0116] The chemical composition of the frit is composed of the following components by weight percentage:

[0117] SiO2 52.17%, Al2O3 5.19%, K2O 0.48%, Na2O 4.85%, CaO 9.02%, MgO 1.82%, Fe2O3 0.12%, B2O3 2.88%, BaO 8.22%, ZnO 14.16%, ignition loss 1.09%.

[0118] The glaze of this embodiment is made of transparent frit, the glaze slurry fineness after processing is 0.3% (325 mesh sieve residue), the glaze slurry specific gravity is controlled to be 1.65g / mL, and the product glazing amount (300×300mm specification plate) is 27g.

[0119] Step B5, after the glaze process is completed, the green body is dried and then put into a roller kiln for firing at a temperature of 1080° C. for 35 minutes to produce a semi-finished product;

[0120] The glaze of this embodiment is sintered at a temperature of 1080°C to obtain a polished tile with a smooth glaze surface, high transparency, a glossiness of 30°, and a Mohs hardness of 3 to 5 after polishing.

[0121] Step B6: The fully polished semi-finished products out of the kiln are edge-grinded, air-dried, inspected, color-separated, graded, and stored.

[0122] The present invention provides a process method for preparing low-temperature, fast-firing, high-strength ceramic black blanks using vanadium-titanium slag. Through the action of a multi-element low-temperature flux, the formula can be quickly sintered at 1060°C to 1100°C to obtain a ceramic product that meets the performance standards. The product has a water absorption rate of less than 0.1, a modulus of rupture of up to 75MPa, and a sintering range of above 30°C.

[0123] The present invention achieves the following effects:

[0124] First, a large amount of vanadium-titanium slag is introduced into the billet, and the addition amount can reach 60% to 70%, which can completely replace the barren raw materials in the billet, such as (potassium and sodium feldspar), slowing down the depletion of mineral resources and greatly improving the utilization rate of vanadium-titanium slag;

[0125] Second, the traditional formula of high-aluminum-reinforced green body formula system was changed to a low-aluminum green body formula system reinforced with metal oxides. The other properties of the product have reached the national standard of traditional ceramic products.

[0126] Third, the characteristics of the formula are that vanadium-titanium slag will undergo complex decomposition reactions at high temperatures. In order to avoid the high-temperature exhaust affecting the body-glaze combination and glaze quality, a matching low-temperature base and surface glaze formula was developed;

[0127] Fourth, a large amount of vanadium-titanium slag is introduced into the green body. The vanadium-titanium slag has a high iron content and contains low-temperature flux components such as Na2O, CaO, MgO, Fe2O3, and MnO, which can greatly reduce the sintering temperature of the green body. The sintering temperature of the ceramic green body can be reduced to 1060°C to 1100°C, and the water absorption rate of the product is below 0.1. Compared with the sintering temperature of about 1180°C to 1240°C of the general ceramic green body formula, the sintering temperature of the present invention can be reduced by 120°C to 140°C, and the sintering temperature has been greatly reduced. The firing cycle is also controlled at 35 minutes, realizing a low-temperature fast-firing ceramic production process and reducing the production cost of ceramic products.

[0128] Fifth, by utilizing the high iron oxide content in vanadium-titanium slag, combined with multi-element low-temperature flux and a special green body structure design of polycrystalline phase, a high-strength ceramic formula system is obtained, with the highest modulus of rupture reaching 75MPa. The modulus of rupture of the product corresponding to the traditional ceramic green body formula is 45MPa, which greatly improves the strength of the ceramic product;

[0129] Sixth, by adding up to 70% vanadium-titanium slag to the billet, we help vanadium-titanium mining companies solve the problem of slag digestion, prevent the huge harm of vanadium-titanium slag to the natural ecology and environment, and achieve green and environmental protection of mineral resources.

[0130] The present invention provides a low-temperature fast-firing ceramic body, a high-strength ceramic brick and a preparation method thereof. The raw materials of the ceramic body include, by weight, 8 to 15 parts of ball clay, 1 to 8 parts of bentonite, 1 to 8 parts of black talc, 60 to 70 parts of vanadium-titanium slag, 8 to 15 parts of kaolin, and 0.3 to 0.5 parts of a body disintegrator. The present invention introduces a large amount of vanadium-titanium slag into the formula of the ceramic body, which can completely replace the barren raw materials in the blank, slow down the depletion of mineral resources, greatly improve the utilization rate of vanadium-titanium slag, avoid waste of resources, and form a low-aluminum body formula system enhanced with metal oxides, which can greatly reduce the sintering temperature of the body, reduce the water absorption rate of the product, shorten the firing cycle, and realize a low-temperature fast-firing ceramic production process.

[0131] It should be understood that the application of the present invention is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A high-strength ceramic brick, characterized in that: include: A ceramic body, a base glaze layer disposed on the ceramic body, a pattern decoration layer disposed on the base glaze layer, and a surface glaze layer disposed on the pattern decoration layer; The raw materials of the ceramic body include, by weight: 8-15 parts of ball clay, 1-8 parts of bentonite, 1-8 parts of black talc, 60-70 parts of vanadium-titanium slag, 8-15 parts of kaolin, 0.3-0.5 parts of green body disintegrator; The chemical components of the ceramic body include, by weight: SiO2 25-35 parts, Al2O3 5-10 parts, K2O 0.2-1.5 parts, Na2O 1-4.5 parts, CaO 1.0-2.5 parts, MgO 1.5-3.5 parts, TiO2 7.5-11.45 parts, Fe2O3 25.5-35.5 parts, Cr2O3 2.5-3.5 parts, MnO 4.5-6.9 parts; The chemical components of the vanadium-titanium slag include, by weight percentage: Loss on ignition 1.16~1.55%, Al2O3 3.5~4.56%, SiO2 12.55~18.05%, Fe2O3 42.65~49.47%, CaO2.05~3.71%, MgO 2.5~3.55%, K2O 0.01~0.05%, Na2O 3.55~5.91%, TiO2 8.95~12.25%, MnO7.85~11.58%, Cr2O3 2.35~5.51%; The raw materials of the base glaze layer include, by weight: 5-10 parts of kaolin, 10-15 parts of quartz, 50-60 parts of albite, 10-15 parts of potassium feldspar, 1-5 parts of calcined talc, 0-5 parts of zirconium silicate, 2-8 parts of calcite, 0.3-0.5 parts of sodium tripolyphosphate, and 0.1-0.2 parts of carboxymethyl cellulose; The chemical components of the base glaze layer include, by weight percentage: SiO255~60%, Al2O315~25%, Na2O 5~8%, K2O 1.5~2.5%, CaO 1~5%, MgO 0.5~1.5%, ZrO2 0.1~0.5%, Fe2O3 0.15~0.3%; The raw materials of the glaze layer include, by weight: 20-30 parts of frit, 5-12 parts of kaolin, 1-3 parts of calcined kaolin, 5-10 parts of quartz, 2-8 parts of barium carbonate, 25-38 parts of albite, 5-8 parts of calcite, 3-9 parts of calcined talc, 3-5 parts of zinc oxide, 0.3-0.5 parts of sodium tripolyphosphate, and 0.1-0.2 parts of carboxymethyl cellulose; The chemical components of the glaze layer include, by weight percentage: SiO245.5~58.89%, Al2O310.5~15.8%, K2O 1.05~1.82%, Na2O3.5~5.44%, CaO 5.5~8.85%, MgO 0.5~3.84%, Fe2O3 0.1~0.36%, B2O30.1~3.25%, BaO 5.5~8.67%, ZnO 4.35~6.72%; The high-strength ceramic brick has a firing temperature of 1060°C to 1100°C, a firing cycle of 35 to 60 minutes, a water absorption rate of less than 0.1%, a rupture modulus of 75 MPa, a glossiness of 25 to 35°, and a Mohs hardness of 3 to 5.

2. The high-strength ceramic brick according to claim 1, characterized in that: The chemical components of the frit include, by weight percentage: SiO245.5~55.72%, Al2O35.0~10.5%, K2O 0.35~3.25%, Na2O3.85~8.45%, CaO 7.5~12.5%, MgO 0.59~3.85%, Fe2O3 0.1~0.25%, B2O32.5~5.55%, BaO 7.5~12.55%, ZnO 10.55~15.52%.

3. A method for preparing a high-strength ceramic tile as claimed in claim 1 or 2, characterized in that: include: The raw materials are mixed and ground according to the formula ratio to obtain a formula slurry that meets the preset fineness, and the formula slurry is sieved, aged, and impurities are removed, and then spray-dried to obtain a powder; The powder is pressed into a shape, dried in a drying kiln to obtain a ceramic body, and a base glaze is applied on the ceramic body to obtain a base glaze layer; Performing inkjet decoration on the base glaze layer to obtain a pattern decoration layer, applying a top glaze on the pattern decoration layer to obtain the top glaze layer and then drying to obtain a glaze blank; The glaze blank is fired at a firing temperature of 1060° C. to 1100° C. and a firing period of 35 to 60 minutes to obtain a high-strength ceramic tile.

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