A method for preparing a glass-ceramic, a glass-ceramic and applications thereof

Abstract

The application relates to the technical field of building materials, and discloses a method for preparing microcrystalline glass, the microcrystalline glass and application thereof. The method comprises the following steps: (1) mixing, melting and cooling heavy-alcohol incineration ash, waste glass, gasification furnace slag, fluxing agent and crystal nucleus agent to obtain glass slag, wherein the melting temperature is 1100-1400 DEG C; (2) mixing, baking and cooling the glass slag and the heavy-alcohol incineration ash to obtain microcrystalline glass, wherein the baking temperature is 800-1000 DEG C. The heavy-alcohol incineration ash with high sodium and low silicon and the gasification furnace slag with high silicon and low calcium are combined according to advantages, the temperature of melting can be reduced, the addition amount of external ores or chemical raw materials can be reduced, the Na-Al-Si system microcrystalline glass can be formed, the heavy-alcohol incineration ash is added again during the sintering process, the sintering temperature can be reduced, and the energy consumption of the microcrystalline glass preparation process can be reduced.

Description

Technical Field

[0001] This invention relates to the field of building materials technology, specifically to a method for preparing microcrystalline glass, microcrystalline glass and its applications. Background Technology

[0002] Glass-ceramics, also known as glass-ceramics or microcrystalline ceramics, are polycrystalline composite materials produced by controlling the crystallization of a base glass with a specific composition during heat treatment. They are characterized by a uniform distribution of glass and microcrystalline phases. Compared to traditional glass, they exhibit higher softening temperatures, superior thermal and chemical stability, and higher mechanical strength and hardness. Compared to ceramics, glass-ceramics have more uniform and dense grains and microstructures, virtually no pores, and a smooth surface. Therefore, glass-ceramics possesses both the basic properties of glass and the polycrystalline characteristics of ceramics, combining the advantages of both. They are a novel inorganic polycrystalline solid material with excellent performance and controllable structural composition.

[0003] The raw materials for microcrystalline glass can be general glass raw materials, or various bulk industrial solid wastes such as slag, tailings, ash, and fly ash. These solid wastes contain silicon, aluminum, calcium, magnesium, iron, and other elements necessary for the preparation of microcrystalline glass. Utilizing these wastes as raw materials to prepare microcrystalline glass can not only reduce environmental pollution but also generate certain economic value. Hazardous waste incineration ash and gasification slag are common hazardous and solid wastes in the petrochemical industry, and their proper disposal is receiving increasing attention. Petrochemical hazardous waste incineration ash contains a large amount of sodium, while gasification slag contains elements such as silicon, calcium, aluminum, and iron. Combining these two materials in a balanced way can yield a suitable ash with a chemical composition that meets the requirements for preparing Na-Ca-Al-Si based microcrystalline glass.

[0004] Currently, common methods for preparing glass-ceramics include the melting method, sintering method, and sol-gel method. The melting method was the earliest and most mature method for preparing glass-ceramics. Its advantages include a simple process, continuous production, and high mechanical properties of the product. Disadvantages include high energy consumption, difficulty in controlling the crystallization process, and a tendency for the product to crack. The sintering method involves grinding the base glass into particles and then sintering the crystals under appropriate heat treatment to obtain glass-ceramics. The sintering method has lower processing temperatures and lower energy consumption, but the product has more internal pores and poor density. The sol-gel method is a novel preparation method. It involves adding certain metal compounds, hydrolyzing them at a lower temperature to generate gel powder, and then transforming the gel powder into glass-ceramics through a specific heat treatment. The crystals in glass-ceramics prepared by the sol-gel method can reach the nanoscale. Disadvantages include high production costs and shrinkage during sintering, which can cause deformation of the glass-ceramics.

[0005] Chinese patent application CN104496186 A discloses a cordierite-based nanocrystalline glass and its preparation method, including a main component, a nucleating agent, a modifier, and a flux. The main component includes SiO2, MgO, and Al2O3; the nucleating agent includes one or more of TiO2, ZrO2, and P2O5, prepared by a melt method, with a nucleation temperature of 500℃~700℃ and a crystallization treatment temperature of 1050~1200℃. Chinese patent application CN102838283 A discloses a method and product for producing foamed microcrystalline glass using composite industrial waste residue. The method involves crushing different industrial waste residues, mixing and grinding them into raw material powder, heating and melting the raw material powder, quenching, drying, and then grinding it into mature material. A nucleating agent, foaming agent, foam stabilizer, flux, and reinforcing agent are then added to form a foamed microcrystalline glass batch. The batch is pressed into shape, and after preheating, foaming, foam stabilizing, and annealing stages, foamed microcrystalline glass is obtained after firing.

[0006] Currently, whether using pure materials or industrial waste to prepare microcrystalline glass, there are problems such as high melting temperature and high production cost, which limit the development of microcrystalline glass. Therefore, how to reduce the production cost of microcrystalline glass is an important problem that the microcrystalline glass industry urgently needs to solve. Summary of the Invention

[0007] The purpose of this invention is to overcome the problems of high melting temperature and high production cost in existing methods for preparing microcrystalline glass. This invention provides a method for preparing microcrystalline glass, microcrystalline glass and its applications. The method combines high-sodium, low-silicon heavy alcohol incineration ash with high-silicon, low-calcium gasification slag, which can reduce the melting temperature. At the same time, the addition of heavy alcohol incineration ash during the sintering process can reduce the sintering temperature, thereby reducing the production cost.

[0008] To achieve the above objectives, the present invention provides a method for preparing microcrystalline glass, the method comprising the following steps:

[0009] (1) Mix, melt, and cool the heavy alcohol incineration ash, waste glass, gasification furnace slag, flux and nucleating agent to obtain glass slag, wherein the melting temperature is 1100~1400℃;

[0010] (2) The glass slag and heavy alcohol incineration ash are mixed, calcined and cooled to obtain microcrystalline glass, wherein the calcination temperature is 800-1000℃.

[0011] The heavy alcohol incineration ash contains 50-85% by weight of Na2CO3 and 5-20% by weight of SiO2.

[0012] The gasification slag contains 20-45% by weight SiO2, 10-25% by weight CaO and 8-15% by weight Al2O3.

[0013] Preferably, the heavy alcohol incineration ash contains 50-85% by weight Na2CO3, 5-20% by weight SiO2, 5-10% by weight NaCl and 2-10% by weight Fe2O3.

[0014] Preferably, the gasification slag contains 20-45% by weight SiO2, 10-25% by weight CaO, 8-15% by weight Al2O3, 5-15% by weight Fe2O3 and 3-37% by weight residual carbon.

[0015] Preferably, in step (1), based on the total weight of heavy alcohol incineration ash, waste glass, gasification furnace slag, flux, and nucleating agent, the content of the heavy alcohol incineration ash is 20-40% by weight, the content of the waste glass is 25-30% by weight, the content of the gasification furnace slag is 25-30% by weight, the content of the flux is 5-10% by weight, and the content of the nucleating agent is 5-10% by weight.

[0016] Preferably, in step (1), the flux is selected from one or more of B2O3, Na2O, K2O, CaO and BaO.

[0017] Preferably, in step (1), the nucleating agent is selected from one or more of Fe2O3, ZrO2, NaF, Cr2O3 and TiO2.

[0018] Preferably, in step (1), the melting conditions include: a melting temperature of 1200-1300℃; a melting time of 30-150 min, preferably 60-120 min; and a heating rate of 5-20℃ / min, preferably 10-15℃ / min.

[0019] Preferably, step (1) includes: mixing and grinding heavy alcohol incineration ash, waste glass, gasification furnace slag, flux and nucleating agent, and then melting, cooling and drying the resulting raw powder to obtain glass slag.

[0020] Preferably, the particle size of the raw powder obtained by grinding is 25-106 μm, and more preferably 45-75 μm.

[0021] Preferably, the cooling method is water quenching or natural cooling.

[0022] Preferably, the drying temperature is 90–120°C.

[0023] Preferably, in step (2), based on the total weight of glass slag and heavy alcohol incineration ash, the content of glass slag is 65-95% by weight, and the content of heavy alcohol incineration ash is 5-35% by weight.

[0024] Preferably, the calcination conditions include: a calcination temperature of 850–950°C; a calcination time of 60–150 min, preferably 90–120 min; and a heating rate of 5–15°C / min, preferably 8–10°C / min.

[0025] Preferably, step (2) includes: mixing the glass slag and heavy alcohol incineration ash and grinding them, then calcining and cooling the resulting glass composite ash to obtain microcrystalline glass.

[0026] Preferably, the particle size of the glass composite ash obtained by grinding is 25–106 μm, and more preferably 45–75 μm.

[0027] A second aspect of the present invention provides a microcrystalline glass prepared by the method described in the first aspect above.

[0028] Preferably, the density of the microcrystalline glass is 2.08–2.43 g / cm³. 3 Its Vickers hardness is 4.01–4.43 GPa, and its compressive strength is 223–261 MPa.

[0029] The third aspect of the present invention provides an application of the microcrystalline glass described in the second aspect above as a building decoration material.

[0030] This invention utilizes a superior combination of high-sodium, low-silicon heavy alcohol incineration ash and high-silicon, low-calcium gasification slag to prepare base glass. This combination lowers the melting temperature and is more conducive to the formation of Na-Al-Si microcrystalline glass, reducing the need for additional foreign ores or chemical raw materials. Under preferred conditions, adding B2O3 as a flux and TiO2 as a nucleating agent during base glass preparation further lowers the melting temperature. Simultaneously, the secondary addition of heavy alcohol incineration ash during sintering lowers the sintering temperature, thus reducing energy consumption in the microcrystalline glass preparation process.

[0031] Compared with the prior art, the present invention has the following advantages:

[0032] 1. Use heavy alcohol incineration ash and gasification furnace slag as raw materials for the production of microcrystalline glass to achieve the harmless, reduced-volume and resource-based treatment of heavy alcohol incineration ash and gasification furnace slag.

[0033] 2. Combining high-sodium, low-silicon heavy alcohol incineration ash with high-silicon, low-calcium gasification slag is more conducive to the formation of Na-Al-Si microcrystalline glass, which can reduce the amount of foreign ore or chemical raw materials added.

[0034] 3. Adding high-sodium heavy alcohol incineration ash during the sintering process helps reduce energy consumption in the preparation of microcrystalline glass. Attached Figure Description

[0035] Figure 1 This is a flowchart of the preparation of microcrystalline glass according to the present invention. Detailed Implementation

[0036] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0037] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0038] The first aspect of this invention provides a method for preparing glass-ceramics, the method comprising the following steps:

[0039] (1) Mix, melt, and cool the heavy alcohol incineration ash, waste glass, gasification furnace slag, flux and nucleating agent to obtain glass slag, wherein the melting temperature is 1100~1400℃;

[0040] (2) The glass slag and heavy alcohol incineration ash are mixed, calcined and cooled to obtain microcrystalline glass, wherein the calcination temperature is 800-1000℃.

[0041] In the method described in this invention, the synergistic effect of heavy alcohol incineration ash containing specific components and gasification slag containing specific components, mixed with waste glass, flux, and nucleating agent, prepares glass slag (base glass), which can reduce the melting temperature and lower costs. Furthermore, adding heavy alcohol incineration ash again when further calcining the glass slag to prepare microcrystalline glass can further reduce the calcination temperature.

[0042] According to the present invention, specifically, the heavy alcohol incineration ash contains 50-85% by weight of Na2CO3 and 5-20% by weight of SiO2; the gasification slag contains 20-45% by weight of SiO2, 10-25% by weight of CaO and 8-15% by weight of Al2O3.

[0043] More specifically, the heavy alcohol incineration ash mainly contains 50-85% by weight Na₂CO₃, 5-20% by weight SiO₂, 5-10% by weight NaCl, and 2-10% by weight Fe₂O₃. In addition, the heavy alcohol incineration ash also contains small amounts of other components, such as K₂O, Al₂O₃, and MgO.

[0044] More specifically, the gasification slag mainly contains 20-45% by weight SiO2, 10-25% by weight CaO, 8-15% by weight Al2O3, 5-15% by weight Fe2O3 and 3-37% by weight residual carbon.

[0045] In the method described in this invention, the waste glass is common waste glass in the art, and its source is not limited. Specifically, the waste glass contains SiO2, CaO, Na2O, Al2O3, and MgO.

[0046] In the method described in this invention, in order to obtain microcrystalline glass with density, hardness and strength that meet the standards, the amounts of heavy alcohol incineration ash, waste glass, gasification slag, flux and nucleating agent need to be limited to a suitable range.

[0047] In some preferred embodiments, in step (1), based on the total weight of heavy alcohol incineration ash, waste glass, gasification slag, flux, and nucleating agent, the content of the heavy alcohol incineration ash is 20-40% by weight, the content of the waste glass is 25-30% by weight, the content of the gasification slag is 25-30% by weight, the content of the flux is 5-10% by weight, and the content of the nucleating agent is 5-10% by weight.

[0048] According to the present invention, the flux can be any conventionally selected in the art, as long as it can achieve the fluxing effect.

[0049] In a specific embodiment, in step (1), the flux is selected from one or more of B2O3, Na2O, K2O, CaO, and BaO. In a preferred embodiment, to further reduce the melting temperature, the flux is B2O3.

[0050] In this invention, in a specific embodiment, in step (1), the nucleating agent is selected from one or more of Fe2O3, ZrO2, NaF, Cr2O3, and TiO2. In a preferred embodiment, in step (1), the nucleating agent is Fe2O3 or TiO2.

[0051] In this invention, the combination of high-sodium, low-silicon heavy alcohol incineration ash and high-silicon, low-calcium gasification slag is more conducive to the formation of Na-Al-Si microcrystalline glass, and the melting temperature is reduced.

[0052] In a specific embodiment, in step (1), the melting temperature can be 1100℃, 1150℃, 1200℃, 1250℃, 1300℃, 1350℃ or 1400℃; preferably, the melting temperature is 1200~1300℃.

[0053] According to the present invention, in step (1), the melting time can be selected conventionally in the art. In a preferred embodiment, the melting time is 30 to 150 min, preferably 60 to 120 min, specifically, for example, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min or 120 min.

[0054] In this invention, the melting process may include: heating to the melting temperature at a certain heating rate, and then holding at the melting temperature for a melting time. Specifically, the heating rate may be 5 to 20 °C / min, preferably 10 to 15 °C / min, for example 10 °C / min, 11 °C / min, 12 °C / min, 13 °C / min, 14 °C / min or 15 °C / min.

[0055] In a preferred embodiment, step (1) specifically includes: mixing and grinding heavy alcohol incineration ash, waste glass, gasification furnace slag, flux and nucleating agent, and then melting, cooling and drying the obtained raw powder to obtain glass slag.

[0056] According to the present invention, specifically, the grinding process is carried out in a planetary ball mill. In a specific embodiment, the particle size of the raw powder obtained by grinding is 25–106 μm, preferably 45–75 μm.

[0057] According to the present invention, the cooling method can be any cooling method well known in the art. Specifically, the cooling method can be water quenching or natural cooling. In a preferred embodiment, water quenching is used to improve the rigidity and compressive strength of the prepared microcrystalline glass.

[0058] In this invention, the drying method can be a conventional operation in the art, such as drying to constant weight in a forced-air drying oven. In this invention, the drying temperature can be a conventional selection in the art; specifically, the drying temperature can be 90–120°C, for example, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, or 120°C.

[0059] In the method of the present invention, in order to reduce the calcination temperature without affecting the density, compressive strength and hardness of the glass-ceramic, in a preferred embodiment, in step (2), the content of the glass slag is 65-95% by weight and the content of the heavy alcohol incineration ash is 5-35% by weight, based on the total weight of the glass slag and the heavy alcohol incineration ash.

[0060] According to the present invention, the calcination temperature can be reduced by adding high-sodium heavy alcohol incineration ash. In a specific embodiment, the calcination temperature in step (2) can be 800-1000℃; preferably, the calcination temperature is 850-950℃, for example 850℃, 860℃, 870℃, 880℃, 890℃, 900℃, 910℃, 920℃, 930℃, 940℃ or 950℃.

[0061] In a specific embodiment, in step (2), the roasting time can be 60 to 150 min, preferably 90 to 120 min, such as 90 min, 95 min, 100 min, 105 min, 110 min, 115 min or 120 min.

[0062] In this invention, the calcination process includes: heating to the calcination temperature at a certain heating rate, and then holding the temperature at the calcination temperature for a certain calcination time. Specifically, the heating rate can be 5 to 15°C / min, preferably 8 to 10°C / min, for example 8°C / min, 8.5°C / min, 9°C / min, 9.5°C / min or 10°C / min.

[0063] In a preferred embodiment, step (2) includes: mixing the glass slag and heavy alcohol incineration ash and grinding them, then calcining and cooling the resulting glass composite ash to obtain microcrystalline glass.

[0064] In this invention, the grinding can be performed using conventional equipment in the art; specifically, the grinding is carried out in a planetary ball mill.

[0065] In a specific embodiment, the particle size of the glass composite ash obtained by grinding can be 25-106 μm, preferably 45-75 μm.

[0066] A second aspect of the present invention provides a microcrystalline glass prepared by the method described in the second aspect above.

[0067] In a preferred embodiment, the density of the microcrystalline glass is 2.08–2.43 g / cm³. 3 Its Vickers hardness is 4.01–4.43 GPa, and its compressive strength is 223–261 MPa.

[0068] The third aspect of the present invention provides an application of the microcrystalline glass described in the second aspect above as a building decoration material.

[0069] The present invention will be described in detail below through embodiments, but the scope of protection of the present invention is not limited thereto.

[0070] Unless otherwise specified, all reagents mentioned in the following examples are commercially available. The waste glass contained 72.23% by weight SiO2, 13.94% by weight CaO, 8.20% by weight Na2O, 2.92% by weight MgO, and 1.07% by weight Al2O3.

[0071] Example 1

[0072] In this embodiment, the heavy alcohol incineration ash contains 75% by weight Na2CO3, 15% by weight SiO2, 5% by weight NaCl and 3% by weight Fe2O3.

[0073] The gasification slag contains 41% by weight SiO2, 15% by weight CaO, 15% by weight Al2O3, 15% by weight Fe2O3 and 3% by weight residual carbon.

[0074] Methods for preparing microcrystalline glass include:

[0075] (1) Mix 30g of heavy alcohol incineration ash, 25g of waste glass, 30g of gasification furnace slag, 10g of B2O3 and 5g of TiO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0076] (2) The raw material powder is heated to 1300°C at a heating rate of 10°C / min and held for 90 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0077] (3) Place the glass slag in a 105℃ forced-air drying oven and dry it to constant weight;

[0078] (4) Mix 80g of glass slag and 20g of heavy alcohol incineration ash and grind them in a planetary ball mill until the particle size is 45-58μm to obtain clinker powder.

[0079] (5) The calcined powder is placed in a corundum crucible and heated to 900°C at a heating rate of 8°C / min, held for 90 min, and then cooled naturally to obtain microcrystalline glass.

[0080] Example 2

[0081] In this embodiment, the heavy alcohol incineration ash contains 75% by weight Na2CO3, 15% by weight SiO2, 5% by weight NaCl and 3% by weight Fe2O3.

[0082] The gasification slag contains 41% by weight SiO2, 15% by weight CaO, 15% by weight Al2O3, 15% by weight Fe2O3 and 3% by weight residual carbon.

[0083] Methods for preparing microcrystalline glass include:

[0084] (1) Mix 35g of heavy alcohol incineration ash, 25g of waste glass, 25g of gasification furnace slag, 10g of B2O3 and 5g of TiO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0085] (2) The raw material powder is heated to 1300°C at a heating rate of 10°C / min and held for 90 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0086] (3) Place the glass slag in a 105℃ forced-air drying oven and dry it to constant weight;

[0087] (4) Mix 80g of glass slag and 20g of heavy alcohol incineration ash and grind them in a planetary ball mill until the particle size is 45-58μm to obtain clinker powder.

[0088] (5) The calcined powder is placed in a corundum crucible and heated to 900°C at a heating rate of 8°C / min, held for 90 min, and then cooled naturally to obtain microcrystalline glass.

[0089] Example 3

[0090] In this embodiment, the heavy alcohol incineration ash contains 75% by weight Na2CO3, 15% by weight SiO2, 5% by weight NaCl and 3% by weight Fe2O3.

[0091] The gasification slag contains 41% by weight SiO2, 15% by weight CaO, 15% by weight Al2O3, 15% by weight Fe2O3 and 3% by weight residual carbon.

[0092] Methods for preparing microcrystalline glass include:

[0093] (1) Mix 30g of heavy alcohol incineration ash, 25g of waste glass, 25g of gasification furnace slag, 10g of B2O3 and 10g of TiO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0094] (2) The raw material powder is heated to 1300°C at a heating rate of 10°C / min and held for 90 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0095] (3) Place the glass slag in a 105℃ forced-air drying oven and dry it to constant weight;

[0096] (4) Mix 80g of glass slag and 20g of heavy alcohol incineration ash and grind them in a planetary ball mill until the particle size is 45-58μm to obtain clinker powder.

[0097] (5) The calcined powder is placed in a corundum crucible and heated to 900°C at a heating rate of 8°C / min, held for 90 min, and then cooled naturally to obtain microcrystalline glass.

[0098] Example 4

[0099] In this embodiment, the heavy alcohol incineration ash contains 75% by weight Na2CO3, 15% by weight SiO2, 5% by weight NaCl and 3% by weight Fe2O3.

[0100] The gasification slag contains 41% by weight SiO2, 15% by weight CaO, 15% by weight Al2O3, 15% by weight Fe2O3 and 3% by weight residual carbon.

[0101] Methods for preparing microcrystalline glass include:

[0102] (1) Mix 30g of heavy alcohol incineration ash, 25g of waste glass, 30g of gasification furnace slag, 10g of B2O3 and 5g of TiO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0103] (2) The raw material powder is heated to 1400°C at a heating rate of 10°C / min and held for 90 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0104] (3) Place the glass slag in a 105℃ forced-air drying oven and dry it to constant weight;

[0105] (4) Mix 80g of glass slag and 20g of heavy alcohol incineration ash and grind them in a planetary ball mill until the particle size is 45-58μm to obtain clinker powder.

[0106] (5) The calcined powder is placed in a corundum crucible and heated to 900°C at a heating rate of 8°C / min, held for 90 min, and then cooled naturally to obtain microcrystalline glass.

[0107] Example 5

[0108] In this embodiment, the heavy alcohol incineration ash contains 75% by weight Na2CO3, 15% by weight SiO2, 5% by weight NaCl and 3% by weight Fe2O3.

[0109] The gasification slag contains 41% by weight SiO2, 15% by weight CaO, 15% by weight Al2O3, 15% by weight Fe2O3 and 3% by weight residual carbon.

[0110] Methods for preparing microcrystalline glass include:

[0111] (1) Mix 30g of heavy alcohol incineration ash, 25g of waste glass, 30g of gasification furnace slag, 10g of B2O3 and 5g of TiO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0112] (2) The raw material powder is heated to 1100°C at a heating rate of 10°C / min and held for 90 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0113] (3) Place the glass slag in a 105℃ forced-air drying oven and dry it to constant weight;

[0114] (4) Mix 80g of glass slag and 20g of heavy alcohol incineration ash and grind them in a planetary ball mill until the particle size is 45-58μm to obtain clinker powder.

[0115] (5) The calcined powder is placed in a corundum crucible and heated to 900°C at a heating rate of 8°C / min, held for 90 min, and then cooled naturally to obtain microcrystalline glass.

[0116] Example 6

[0117] In this embodiment, the heavy alcohol incineration ash contains 75% by weight Na2CO3, 15% by weight SiO2, 5% by weight NaCl and 3% by weight Fe2O3.

[0118] The gasification slag contains 41% by weight SiO2, 15% by weight CaO, 15% by weight Al2O3, 15% by weight Fe2O3 and 3% by weight residual carbon.

[0119] Methods for preparing microcrystalline glass include:

[0120] (1) Mix 30g of heavy alcohol incineration ash, 30g of waste glass, 30g of gasification furnace slag, 5g of B2O3 and 5g of TiO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0121] (2) The raw material powder is heated to 1300°C at a heating rate of 10°C / min and held for 90 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0122] (3) Place the glass slag in a 105℃ forced-air drying oven and dry it to constant weight;

[0123] (4) Mix 90g of glass slag and 10g of heavy alcohol incineration ash and grind them in a planetary ball mill until the particle size is 45-58μm to obtain clinker powder.

[0124] (5) The calcined powder is placed in a corundum crucible and heated to 900°C at a heating rate of 8°C / min, held for 90 min, and then cooled naturally to obtain microcrystalline glass.

[0125] Example 7

[0126] In this embodiment, the heavy alcohol incineration ash contains 75% by weight Na2CO3, 15% by weight SiO2, 5% by weight NaCl and 3% by weight Fe2O3.

[0127] The gasification slag contains 41% by weight SiO2, 15% by weight CaO, 15% by weight Al2O3, 15% by weight Fe2O3 and 3% by weight residual carbon.

[0128] Methods for preparing microcrystalline glass include:

[0129] (1) Mix 30g of heavy alcohol incineration ash, 30g of waste glass, 30g of gasification furnace slag, 5g of B2O3 and 5g of TiO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0130] (2) The raw material powder is heated to 1400°C at a heating rate of 10°C / min and held for 90 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0131] (3) Place the glass slag in a 105℃ forced-air drying oven and dry it to constant weight;

[0132] (4) Mix 70g of glass slag and 30g of heavy alcohol incineration ash and grind them in a planetary ball mill until the particle size is 45-58μm to obtain clinker powder;

[0133] (5) The calcined powder is placed in a corundum crucible and heated to 900°C at a heating rate of 8°C / min, held for 90 min, and then cooled naturally to obtain microcrystalline glass.

[0134] Example 8

[0135] In this embodiment, the heavy alcohol incineration ash contains 75% by weight Na2CO3, 15% by weight SiO2, 5% by weight NaCl and 3% by weight Fe2O3.

[0136] The gasification slag contains 41% by weight SiO2, 15% by weight CaO, 15% by weight Al2O3, 15% by weight Fe2O3 and 3% by weight residual carbon.

[0137] Methods for preparing microcrystalline glass include:

[0138] (1) Mix 30g of heavy alcohol incineration ash, 30g of waste glass, 30g of gasification furnace slag, 5g of CaO and 5g of TiO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0139] (2) The raw material powder is heated to 1300°C at a heating rate of 10°C / min and held for 90 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0140] (3) Place the glass slag in a 105℃ forced-air drying oven and dry it to constant weight;

[0141] (4) Mix 80g of glass slag and 20g of heavy alcohol incineration ash and grind them in a planetary ball mill until the particle size is 45-58μm to obtain clinker powder.

[0142] (5) The calcined powder is placed in a corundum crucible and heated to 900°C at a heating rate of 8°C / min, held for 90 min, and then cooled naturally to obtain microcrystalline glass.

[0143] Example 9

[0144] In this embodiment, the heavy alcohol incineration ash contains 75% by weight Na2CO3, 15% by weight SiO2, 5% by weight NaCl and 3% by weight Fe2O3.

[0145] The gasification slag contains 41% by weight SiO2, 15% by weight CaO, 15% by weight Al2O3, 15% by weight Fe2O3 and 3% by weight residual carbon.

[0146] Methods for preparing microcrystalline glass include:

[0147] (1) Mix 30g of heavy alcohol incineration ash, 30g of waste glass, 30g of gasification furnace slag, 5g of B2O3 and 5g of ZrO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0148] (2) The raw material powder is heated to 1300°C at a heating rate of 10°C / min and held for 90 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0149] (3) Place the glass slag in a 105℃ forced-air drying oven and dry it to constant weight;

[0150] (4) Mix 80g of glass slag and 20g of heavy alcohol incineration ash and grind them in a planetary ball mill until the particle size is 45-58μm to obtain clinker powder.

[0151] (5) The calcined powder is placed in a corundum crucible and heated to 900°C at a heating rate of 8°C / min, held for 90 min, and then cooled naturally to obtain microcrystalline glass.

[0152] Example 10

[0153] In this embodiment, the heavy alcohol incineration ash contains 75% by weight Na2CO3, 15% by weight SiO2, 5% by weight NaCl and 3% by weight Fe2O3.

[0154] The gasification slag contains 41% by weight SiO2, 15% by weight CaO, 15% by weight Al2O3, 15% by weight Fe2O3 and 3% by weight residual carbon.

[0155] Methods for preparing microcrystalline glass include:

[0156] (1) Mix 30g of heavy alcohol incineration ash, 30g of waste glass, 30g of gasification furnace slag, 5g of CaO and 5g of TiO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0157] (2) The raw material powder is heated to 1300°C at a heating rate of 10°C / min and held for 120 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0158] (3) Place the glass slag in a 110℃ forced-air drying oven and dry it to constant weight;

[0159] (4) Mix 80g of glass slag and 20g of heavy alcohol incineration ash and grind them in a planetary ball mill until the particle size is 45-58μm to obtain clinker powder.

[0160] (5) The calcined powder is placed in a corundum crucible and heated to 900°C at a heating rate of 5°C / min, held for 90 min, and then cooled naturally to obtain microcrystalline glass.

[0161] Example 11

[0162] In this embodiment, the heavy alcohol incineration ash contains 75% by weight Na2CO3, 15% by weight SiO2, 5% by weight NaCl and 3% by weight Fe2O3.

[0163] The gasification slag contains 41% by weight SiO2, 15% by weight CaO, 15% by weight Al2O3, 15% by weight Fe2O3 and 3% by weight residual carbon.

[0164] Methods for preparing microcrystalline glass include:

[0165] (1) Mix 30g of heavy alcohol incineration ash, 30g of waste glass, 30g of gasification furnace slag, 5g of CaO and 5g of TiO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0166] (2) The raw material powder is heated to 1300°C at a heating rate of 10°C / min and held for 120 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0167] (3) Place the glass slag in a 110℃ forced-air drying oven and dry it to constant weight;

[0168] (4) Mix 80g of glass slag and 20g of heavy alcohol incineration ash and grind them in a planetary ball mill until the particle size is 45-58μm to obtain clinker powder.

[0169] (5) The calcined powder is placed in a corundum crucible and heated to 900°C at a heating rate of 10°C / min. The temperature is held for 90 min and then cooled naturally to obtain microcrystalline glass.

[0170] Example 12

[0171] In this embodiment, the heavy alcohol incineration ash contains 75% by weight Na2CO3, 15% by weight SiO2, 5% by weight NaCl and 3% by weight Fe2O3.

[0172] The gasification slag contains 41% by weight SiO2, 15% by weight CaO, 15% by weight Al2O3, 15% by weight Fe2O3 and 3% by weight residual carbon.

[0173] Methods for preparing microcrystalline glass include:

[0174] (1) Mix 30g of heavy alcohol incineration ash, 30g of waste glass, 30g of gasification furnace slag, 5g of CaO and 5g of TiO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0175] (2) The raw material powder is heated to 1300°C at a heating rate of 10°C / min and held for 120 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0176] (3) Place the glass slag in a 110℃ forced-air drying oven and dry it to constant weight;

[0177] (4) Mix 80g of glass slag and 20g of heavy alcohol incineration ash and grind them in a planetary ball mill until the particle size is 45-58μm to obtain clinker powder.

[0178] (5) The calcined powder is placed in a corundum crucible and heated to 800°C at a heating rate of 8°C / min, held for 120 min, and then cooled naturally to obtain microcrystalline glass.

[0179] Comparative Example 1

[0180] The method was implemented according to Example 1, except that the heavy alcohol incineration ash in steps (1) and (4) was replaced with pure Na2CO3.

[0181] In this comparative example, the gasification slag contains 41% by weight SiO2, 15% by weight CaO, 15% by weight Al2O3, 15% by weight Fe2O3 and 3% by weight residual carbon.

[0182] Methods for preparing microcrystalline glass include:

[0183] (1) Mix 30g of sodium carbonate, 25g of waste glass, 30g of gasification slag, 10g of B2O3 and 5g of TiO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0184] (2) The raw material powder is heated to 1300°C at a heating rate of 10°C / min and held for 90 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0185] (3) Place the glass slag in a 105℃ forced-air drying oven and dry it to constant weight;

[0186] (4) Mix 80g of glass slag and 20g of sodium carbonate and grind them in a planetary ball mill until the particle size is 45-58μm to obtain clinker powder;

[0187] (5) The calcined powder is placed in a corundum crucible and heated to 900°C at a heating rate of 8°C / min, held for 90 min, and then cooled naturally to obtain microcrystalline glass.

[0188] Comparative Example 2

[0189] The method was implemented according to Example 1, except that the heavy alcohol incineration ash in step (1) was replaced with pure Na2CO3.

[0190] In this embodiment, the heavy alcohol incineration ash contains 75% by weight Na2CO3, 15% by weight SiO2, 5% by weight NaCl and 3% by weight Fe2O3.

[0191] The gasification slag contains 41% by weight SiO2, 15% by weight CaO, 15% by weight Al2O3, 15% by weight Fe2O3 and 3% by weight residual carbon.

[0192] Methods for preparing microcrystalline glass include:

[0193] (1) Mix 30g of sodium carbonate, 25g of waste glass, 30g of gasification slag, 10g of B2O3 and 5g of TiO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0194] (2) The raw material powder is heated to 1300°C at a heating rate of 10°C / min and held for 90 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0195] (3) Place the glass slag in a 105℃ forced-air drying oven and dry it to constant weight;

[0196] (4) Mix 80g of glass slag and 20g of heavy alcohol incineration ash and grind them in a planetary ball mill until the particle size is 45-58μm to obtain clinker powder.

[0197] (5) The calcined powder is placed in a corundum crucible and heated to 900°C at a heating rate of 8°C / min, held for 90 min, and then cooled naturally to obtain microcrystalline glass.

[0198] Comparative Example 3

[0199] The method was implemented according to Example 1, except that the heavy alcohol incineration ash in step (4) was replaced with pure Na2CO3.

[0200] In this embodiment, the heavy alcohol incineration ash contains 75% by weight Na2CO3, 15% by weight SiO2, 5% by weight NaCl and 3% by weight Fe2O3.

[0201] The gasification slag contains 41% by weight SiO2, 15% by weight CaO, 15% by weight Al2O3, 15% by weight Fe2O3 and 3% by weight residual carbon.

[0202] Methods for preparing microcrystalline glass include:

[0203] (1) Mix 30g of heavy alcohol incineration ash, 25g of waste glass, 30g of gasification furnace slag, 10g of B2O3 and 5g of TiO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0204] (2) The raw material powder is heated to 1300°C at a heating rate of 10°C / min and held for 90 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0205] (3) Place the glass slag in a 105℃ forced-air drying oven and dry it to constant weight;

[0206] (4) Mix 80g of glass slag and 20g of sodium carbonate and grind them in a planetary ball mill until the particle size is 45-58μm to obtain clinker powder;

[0207] (5) The calcined powder is placed in a corundum crucible and heated to 900°C at a heating rate of 8°C / min, held for 90 min, and then cooled naturally to obtain microcrystalline glass.

[0208] Comparative Example 4

[0209] The method is implemented according to Example 1, except that no heavy alcohol incineration ash is added in step (4).

[0210] In this embodiment, the heavy alcohol incineration ash contains 75% by weight Na2CO3, 15% by weight SiO2, 5% by weight NaCl and 3% by weight Fe2O3.

[0211] The gasification slag contains 41% by weight SiO2, 15% by weight CaO, 15% by weight Al2O3, 15% by weight Fe2O3 and 3% by weight residual carbon.

[0212] Methods for preparing microcrystalline glass include:

[0213] (1) Mix 30g of heavy alcohol incineration ash, 25g of waste glass, 30g of gasification furnace slag, 10g of B2O3 and 5g of TiO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0214] (2) The raw material powder is heated to 1300°C at a heating rate of 10°C / min and held for 90 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0215] (3) Place the glass slag in a 105℃ forced-air drying oven and dry it to constant weight;

[0216] (4) Place 80g of glass slag on a planetary ball mill and grind it to a particle size of 45-58μm to obtain clinker powder;

[0217] (5) The calcined powder is placed in a corundum crucible and heated to 900°C at a heating rate of 8°C / min, held for 90 min, and then cooled naturally to obtain microcrystalline glass.

[0218] Comparative Example 5

[0219] The method is implemented according to Example 1, except that no heavy alcohol incineration ash is added in step (1).

[0220] In this embodiment, the heavy alcohol incineration ash contains 75% by weight Na2CO3, 15% by weight SiO2, 5% by weight NaCl and 3% by weight Fe2O3.

[0221] The gasification slag contains 41% by weight SiO2, 15% by weight CaO, 15% by weight Al2O3, 15% by weight Fe2O3 and 3% by weight residual carbon.

[0222] Methods for preparing microcrystalline glass include:

[0223] (1) Mix 25g of waste glass, 30g of gasification slag, 10g of B2O3 and 5g of TiO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0224] (2) The raw material powder is heated to 1300°C at a heating rate of 10°C / min and held for 90 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0225] (3) Place the glass slag in a 105℃ forced-air drying oven and dry it to constant weight;

[0226] (4) Mix 80g of glass slag and 20g of heavy alcohol incineration ash and grind them in a planetary ball mill until the particle size is 45-58μm to obtain clinker powder.

[0227] (5) The calcined powder is placed in a corundum crucible and heated to 900°C at a heating rate of 8°C / min, held for 90 min, and then cooled naturally to obtain microcrystalline glass.

[0228] Comparative Example 6

[0229] The method is implemented according to Example 1, except that gasification slag is not added in step (1).

[0230] In this embodiment, the heavy alcohol incineration ash contains 75% by weight Na2CO3, 15% by weight SiO2, 5% by weight NaCl and 3% by weight Fe2O3.

[0231] Methods for preparing microcrystalline glass include:

[0232] (1) Mix 30g of heavy alcohol incineration ash, 25g of waste glass, 10g of B2O3 and 5g of TiO2 and grind them with a planetary ball mill until the particle size is 45-58μm to obtain raw powder.

[0233] (2) The raw material powder is heated to 1300°C at a heating rate of 10°C / min and held for 90 min. Then the resulting glass melt is quenched by water to obtain glass slag.

[0234] (3) Place the glass slag in a 105℃ forced-air drying oven and dry it to constant weight;

[0235] (4) Mix 80g of glass slag and 20g of heavy alcohol incineration ash and grind them in a planetary ball mill until the particle size is 45-58μm to obtain clinker powder.

[0236] (5) The calcined powder is placed in a corundum crucible and heated to 900°C at a heating rate of 8°C / min, held for 90 min, and then cooled naturally to obtain microcrystalline glass.

[0237] Test Example 1

[0238] The density, hardness, and compressive strength of the microcrystalline glass prepared in Examples 1-12 and Comparative Examples 1-6 were tested, and the results are shown in Table 1.

[0239] The density test method is as follows: the density of the microcrystalline glass sample is measured using the specific gravity bottle method. Test procedure: Weigh the sample (m). 物 The specific gravity of the bottle filled with water is m 水 The specific gravity bottle containing the sample and filled with water has a mass of m. 总 Press to calculate sample density:

[0240]

[0241] The hardness test method is as follows: The hardness of the sample is determined using a Vickers hardness tester. Sample preparation: The sample is inlaid, ground flat, and polished. Test conditions: Load 200g, loading time 10s, 5 measurements are taken and the average value is recorded.

[0242] The method for testing compressive strength is as follows: the compressive strength of the sample is determined using a universal testing machine.

[0243] Table 1

[0244]

[0245]

[0246] As can be seen from Table 1, the density, hardness and strength of the microcrystalline glass prepared according to the method of the present invention are superior to those of the comparative example.

[0247] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method of making a microcrystalline glass, characterized by, The method comprises the following steps: (1) mixing, melting and cooling heavy-alcohol incineration ash, waste glass, gasification furnace slag, fluxing agent and nucleating agent to obtain glass slag, wherein the melting temperature is 1100-1400℃; (2) mixing and calcining the glass slag and the heavy-alcohol incineration ash, and then cooling to obtain microcrystalline glass, wherein the calcination temperature is 800-1000℃; The heavy-alcohol incineration ash contains 50-85 wt% of Na2CO3, 5-20 wt% of SiO2, 5-10 wt% of NaCl and 2-10 wt% of Fe2O3. The gasification furnace slag contains 20-45 wt% of SiO2, 10-25 wt% of CaO, 8-15 wt% of Al2O3, 5-15 wt% of Fe2O3 and 3-37 wt% of residual carbon. In step (1), the content of the heavy-alcohol incineration ash is 20-40 wt%, the content of the waste glass is 25-30 wt%, the content of the gasification furnace slag is 25-30 wt%, the content of the fluxing agent is 5-10 wt%, and the content of the nucleating agent is 5-10 wt%, based on the total weight of the heavy-alcohol incineration ash, the waste glass, the gasification furnace slag, the fluxing agent and the nucleating agent. In step (2), the content of the glass slag is 65-95 wt%, and the content of the heavy-alcohol incineration ash is 5-35 wt%, based on the total weight of the glass slag and the heavy-alcohol incineration ash.

2. The method of claim 1, wherein, In step (1), the fluxing agent is selected from one or more of B2O3, Na2O, K2O, CaO and BaO.

3. The method of claim 1, wherein, In step (1), the nucleating agent is selected from one or more of Fe2O3, ZrO2, NaF, Cr2O3 and TiO2.

4. The method of claim 1, wherein, In step (1), the melting conditions include a melting temperature of 1200-1300℃, a melting time of 30-150 min and a heating rate of 5-20℃ / min.

5. The method of claim 4, wherein, In step (1), the melting conditions include a melting time of 60-120 min.

6. The method of claim 4, wherein, In step (1), the melting conditions include a heating rate of 10-15℃ / min.

7. The method of claim 1, wherein, In step (1), the heavy-alcohol incineration ash, the waste glass, the gasification furnace slag, the fluxing agent and the nucleating agent are mixed and then ground, and then the obtained raw powder is melted, cooled and dried to obtain the glass slag.

8. The method of claim 7, wherein, The particle size of the obtained raw powder is 25-106μm.

9. The method of claim 8, wherein, The particle size of the obtained raw powder is 45-75μm.

10. The method according to claim 7 or 8, characterized in that, The cooling method is water quenching or natural cooling.

11. The method of claim 7 or 8, wherein, The drying temperature is 90-120℃.

12. The method of claim 1, wherein, The calcination conditions include a calcination temperature of 850-950℃, a calcination time of 60-150 min and a heating rate of 5-15℃ / min.

13. The method of claim 12, wherein, The calcination conditions include a calcination time of 90-120 min.

14. The method of claim 12, wherein, The calcination conditions include a heating rate of 8-10℃ / min.

15. The method of claim 1, wherein, In step (2), the glass slag and the heavy-alcohol incineration ash are mixed and then ground, and then the obtained glass composite ash is calcined and cooled to obtain the microcrystalline glass.

16. The method of claim 15, wherein, The particle size of the obtained glass composite ash is 25-106μm.

17. The method of claim 16, wherein, The particle size of the obtained glass composite ash is 45-75 μm.

18. The glass-ceramic prepared by the method of any one of claims 1-17.

19. The glass-ceramic according to claim 18, characterized in that, The density of the microcrystalline glass is 1.87-2.43 g / cm 3 The Vickers hardness is 3.49-4.43 GPa, and the compressive strength is 197-261 MPa.

20. Use of the glass-ceramic of claim 18 or 19 as a building decoration material.

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