An optimized method for directly preparing glass-ceramics from liquid lead-zinc smelting slag

Abstract

The application discloses an optimization method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag, which comprises the following steps: adding a tempering agent into high-temperature liquid lead-zinc smelting slag, obtaining tempered liquid after melting and mixing, and performing annealing or quenching treatment on the tempered liquid to obtain parent glass; and the parent glass is placed at high temperature to perform crystallization or sintering, and the microcrystalline glass is obtained. The application uses solid cold lead-zinc smelting slag as raw material to prepare the microcrystalline glass, and combines the melting method and the sintering method to directly use the liquid lead-zinc smelting slag to prepare the microcrystalline glass, so that the microcrystalline glass has more excellent mechanical properties and low energy consumption.

Description

Technical Field

[0001] This invention belongs to the field of solid waste resource utilization and inorganic non-metallic material preparation technology, and specifically relates to an optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag. Background Technology

[0002] The pyrometallurgical process of lead and zinc produces a large amount of high-temperature liquid slag (LZS), typically at temperatures between 1200-1400℃. This slag is rich in components such as SiO2, Al2O3, CaO, and Fe2O3, providing a material basis for the preparation of microcrystalline glass. However, currently, the main method of utilizing this smelting slag is water quenching and cooling, followed by its use as cement admixtures or roadbed materials. This method has low added value and fails to effectively utilize the large amount of sensible heat it contains.

[0003] Existing methods for preparing microcrystalline glass typically use natural minerals or industrial solid waste as raw materials, requiring multiple processes such as crushing, batching, high-temperature melting, molding, and crystallization heat treatment. These methods are energy-intensive and lengthy. When the raw material is lead-zinc smelting slag, its complex composition, high content of transition metals such as iron and manganese, and poor thermal stability make it prone to problems such as uneven crystallization, excessively rapid crystallization, and phase separation when used directly to prepare microcrystalline glass. This results in a loose material structure, uneven performance, and difficulty in obtaining high-performance products.

[0004] Therefore, how to directly utilize high-temperature liquid smelting slag, avoid its sensible heat loss and high energy consumption from secondary melting, and develop a short-process, low-energy-consumption, high-performance microcrystalline glass preparation process by precisely controlling its composition and structure through online conditioning has become an urgent technical problem to be solved in the field of high-value utilization of solid waste. Summary of the Invention

[0005] This invention aims to overcome the shortcomings of existing technologies and provide an optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag. This invention directly utilizes the high-temperature sensible heat of the liquid smelting slag to temper and homogenize its source chemical composition in its molten state. It also systematically compares two subsequent process paths—melting and sintering—to select the preparation scheme with the best overall performance and lowest energy consumption. By comparing this invention with traditional processes using solid cold slag as raw material, its advantages are highlighted in terms of both energy consumption and material performance, achieving high efficiency, high value, and direct resource utilization of liquid smelting slag.

[0006] To achieve the above objectives, the first aspect of the present invention provides an optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag. The method includes the following steps: adding a conditioning agent to liquid lead-zinc smelting slag at a temperature of 1200-1350℃, holding the temperature for 30-60 minutes, and melting and mixing uniformly to obtain a conditioning liquid; annealing or quenching the conditioning liquid to obtain a base glass; transferring the base glass to a muffle furnace and heating it to a preset temperature at a heating rate of 10℃ / min, holding it at that temperature for 1-4 hours, and then naturally cooling it to room temperature with the furnace temperature to obtain microcrystalline glass.

[0007] In the first aspect, the conditioning agent includes one or more of SiO2, Al2O3, CaO and Fe2O3.

[0008] In the first aspect, the amount of the conditioning agent added is such that the chemical composition of the conditioning solution meets the requirements for preparing a microcrystalline glass with calcium aluminum feldspar as the main crystalline phase.

[0009] In the first aspect, during the annealing process, the tempering liquid is directly poured into a graphite mold preheated to 500°C and transferred to a muffle furnace at 500°C for 1-2 hours, and then naturally cooled to room temperature with the furnace temperature to obtain the mother glass.

[0010] In the first aspect, the preset temperature is 800-1000℃, and the performance parameters of the microcrystalline glass include: density ≥ 2.67 g / cm³. 3 Water absorption ≤0.023%, compressive strength ≥182MPa, flexural strength ≥38 MPa, Vickers hardness ≥744HV.

[0011] In the first aspect, the total energy consumption of obtaining microcrystalline glass through annealing is ≤15kWh.

[0012] In the first aspect, during the quenching process, the tempering liquid is poured into water for water quenching to obtain amorphous metastable glass quenching slag; the amorphous metastable glass quenching slag is placed in an oven at 105°C and dried for 24 hours to obtain a solid; the solid is ball-milled, crushed, and sieved to obtain the parent glass.

[0013] In the first aspect, the ball milling process conditions include: a ball-to-material ratio of 3:1; and a particle size of the parent glass ≤178μm.

[0014] In the first aspect, the preset temperature is 800-1000℃, and the performance parameters of the microcrystalline glass include: bulk density ≥2.07 g / cm³. 3 Water absorption ≤0.5%, compressive strength ≥62.84 MPa, flexural strength ≥12 MPa, Vickers hardness ≥458 HV.

[0015] In the first aspect, the total energy consumption of obtaining microcrystalline glass through quenching treatment is ≤54kWh.

[0016] In the research process of directly preparing microcrystalline glass from liquid lead-zinc smelting slag, this invention systematically compared two typical process routes: sintering and melting. Through process parameter optimization and performance evaluation, an optimized direct preparation route centered on melt tempering-melting method was ultimately formed. Compared with traditional methods, this invention has the following beneficial effects: (1) Traditional sintering methods use powder as raw material to achieve crystallization and bonding under solid-state conditions, which easily leads to uneven nucleus formation, loose bonding, and high porosity. The microcrystalline glass prepared by the sintering method of this invention has a complex crystal structure with iron diopside as the main crystalline phase and calcium aluminum feldspar as the secondary crystalline phase. This invention achieves dynamic homogenization of melt composition and structure by melting and tempering liquid smelting slag, making the nucleation and crystallization process controllable at the molecular level. The final microcrystalline glass is a single-phase calcium aluminum feldspar with uniform distribution, dense structure, and significantly improved mechanical properties.

[0017] (2) Traditional sintering routes require melting and quenching the solid smelting slag in water before secondary sintering and crystallization, which is cumbersome and energy-intensive. This invention utilizes in-situ conditioning of liquid slag, eliminating the solid crushing-remelting-forming process, and achieves one-time forming and one-step crystallization, which greatly reduces energy consumption and equipment load.

[0018] (3) At the same crystallization temperature, the sample prepared by the melting method has fine and uniform grains, dense Vickers structure without obvious pores, and its bending strength is increased by about 30% and its hardness is increased by about 25%. In contrast, the sample prepared by the sintering method is prone to discontinuous interfaces and pores, and its mechanical strength is significantly lower.

[0019] (4) The sintering method has high requirements for powder particle size and uniformity of batching, which is not conducive to the direct application of liquid slag. The melt tempering method in this invention can adjust the proportion of tempering agent according to the real-time composition changes of liquid slag at the smelting site, realize online process adaptation and continuous preparation, and has the potential for industrial promotion.

[0020] (5) The optimized method of the present invention not only realizes the high-value and direct utilization of liquid lead-zinc smelting slag, but also shows outstanding performance in terms of energy consumption reduction, performance improvement, resource recycling and environmental benefits, and significantly increases the added value of the products. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of this specification or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 This is a flowchart of an optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag according to the present invention; Figure 2 The XRD patterns of the microcrystalline glass prepared by the melting method in Examples 1-4 of this invention are shown. Figure 3 The XRD patterns of the microcrystalline glass prepared by the sintering method in Examples 5-7 of this invention are shown. Figure 4 The XRD patterns are of the microcrystalline glass prepared in Examples 8-9 of this invention. Detailed Implementation

[0023] The advantages and various effects of the present invention will be more clearly presented below in conjunction with specific embodiments and examples. Those skilled in the art should understand that these specific embodiments and examples are for illustrative purposes only and are not intended to limit the invention.

[0024] Throughout this specification, unless otherwise specified, the terminology used herein should be understood as having the meaning commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In the event of any conflict, this specification shall prevail.

[0025] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be obtained by purchasing them from the market or by existing methods.

[0026] Please see Figure 1 This invention provides an optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag. The method includes the following steps: adding a conditioning agent to liquid lead-zinc smelting slag at a temperature of 1200-1350℃, holding the temperature for 30-60 minutes, and melting and mixing evenly to obtain a conditioning liquid; annealing or quenching the conditioning liquid to obtain a base glass; transferring the base glass to a muffle furnace and heating it to a preset temperature at a heating rate of 10℃ / min, holding it at that temperature for 1-4 hours, and then naturally cooling it to room temperature with the furnace temperature to obtain microcrystalline glass.

[0027] Specifically, this invention involves directly adding a conditioning agent to high-temperature liquid lead-zinc smelting slag, allowing the conditioning agent to be uniformly integrated into the slag. This directly utilizes the enormous sensible heat energy contained in the high-temperature liquid slag discharged from the smelter, requiring only a small amount of energy for heat preservation and mixing. This adjusts the chemical composition of the melt from the source, altering its thermodynamic properties and crystallization kinetics, laying the structural foundation for the subsequent formation of an ideal microcrystalline glass phase. Then, the parent glass is obtained through annealing or quenching, followed by melting or sintering in a muffle furnace to obtain a dense microcrystalline glass with high mechanical strength.

[0028] In some possible embodiments, the conditioning agent includes one or more of SiO2, Al2O3, CaO, and Fe2O3.

[0029] In some possible embodiments, the amount of the conditioning agent added is such that the chemical composition of the conditioning solution meets the requirements for preparing a microcrystalline glass with calcium aluminum feldspar as the main crystalline phase.

[0030] In this application, the composition of the original smelting slag is adjusted by adding a conditioning agent to achieve an ideal composition suitable for forming a microcrystalline glass with calcium aluminum feldspar as the main crystalline phase, thereby controlling the crystallization process. Through the synergistic effect between the conditioning agent components, the complex composition and poor thermal stability of liquid lead-zinc smelting slag are transformed into a high-value-added microcrystalline glass material with controllable composition, dense structure, and excellent performance.

[0031] In some possible embodiments, during the annealing process, the tempering liquid is directly poured into a graphite mold preheated to 500°C and transferred to a muffle furnace at 500°C for 1-2 hours, and then naturally cooled to room temperature with the furnace temperature to obtain the parent glass.

[0032] In some possible embodiments, the preset temperature is 800-1000℃, and the performance parameters of the microcrystalline glass include: density ≥ 2.67 g / cm³. 3 Water absorption ≤0.023%, compressive strength ≥182MPa, flexural strength ≥38 MPa, Vickers hardness ≥744 HV.

[0033] In some possible embodiments, the total energy consumption of obtaining microcrystalline glass through annealing is ≤15kWh.

[0034] In this application, a high-temperature tempering liquid is poured into a graphite mold preheated to 500°C to control the cooling rate, reduce thermal shock, and prevent the surface of the melt from solidifying instantly when poured into a cold mold, which would lead to uneven internal shrinkage and cracking or shattering of the glass. Then, the melt is held at 500°C to ensure uniform temperature inside and outside the melt, and the crystal structure of the glass is maintained during the natural cooling process with the furnace temperature.

[0035] Furthermore, the parent glass is heat-treated at 800-1000℃ to optimize its microstructure, resulting in microcrystalline glass with excellent mechanical properties. This process, in stark contrast to traditional methods using solid cold smelting slag, significantly reduces energy consumption and improves material performance, offering both economic and environmental benefits.

[0036] In some possible embodiments, during the quenching process, the tempering liquid is poured into water for water quenching to obtain amorphous metastable glass quenching slag; the amorphous metastable glass quenching slag is placed in an oven at 105°C and dried for 24 hours to obtain a solid; the solid is ball-milled, crushed, and sieved to obtain the parent glass.

[0037] In this application, the high-temperature tempering liquid is poured into water for cold quenching to suppress the orderly arrangement during the cooling process, and then dried at 105°C for 24 hours to completely remove the moisture from the material, so as to avoid the generation of a large number of pores during subsequent high-temperature sintering, which would seriously affect the density and strength of the product.

[0038] In some possible embodiments, the ball milling process conditions include: a ball-to-material ratio of 3:1; and a particle size of the parent glass ≤178μm.

[0039] Specifically, by ball milling and sieving the dried quenched slag, finer powder with a more uniform particle size distribution is obtained, thereby increasing the powder bulk density of the parent glass and reducing the porosity between particles, resulting in a denser microstructure after sintering.

[0040] In some possible embodiments, the preset temperature is 800-1000℃, and the performance parameters of the microcrystalline glass include: bulk density ≥2.07 g / cm³. 3 Water absorption ≤0.5%, compressive strength ≥62.84 MPa, flexural strength ≥12 MPa, Vickers hardness ≥458 HV.

[0041] In some possible embodiments, the total energy consumption of obtaining microcrystalline glass through quenching treatment is ≤54kWh.

[0042] The present application is further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the application. Experimental methods in the following embodiments that do not specify specific conditions are generally determined according to national standards. If there is no corresponding national standard, then general international standards, conventional conditions, or conditions recommended by the manufacturer are followed.

[0043] The liquid lead-zinc smelting slag used in this embodiment of the invention originates from the high-temperature smelting and reduction stages of the lead-zinc pyrometallurgical process. A typical process flow is as follows: lead-zinc concentrate or lead-zinc-containing secondary resources are batched and then fed into a smelting furnace for oxidative smelting, forming a melt containing elements such as lead, zinc, and iron; subsequently, reduction smelting or fumigation treatment is performed to achieve the enrichment and separation of lead and zinc. During this process, valuable metal migration and phase separation occur, forming a high-temperature molten slag rich in components such as Fe, Si, and Ca, i.e., liquid lead-zinc smelting slag.

[0044] The solid cold lead-zinc smelting slag used in this embodiment of the invention is prepared from liquid smelting slag through a water quenching and rapid cooling process. Specifically, after the high-temperature liquid slag is discharged from the smelting furnace, it is rapidly cooled by a water quenching device, causing the slag to undergo a glass transition and form granular or blocky solid materials, thereby obtaining water-quenched lead-zinc smelting slag.

[0045] The raw materials all come from Minshan Huaneng High-Tech Co., Ltd. in Anyang City, Henan Province. Relying on a continuous lead smelting process system such as "bottom blowing smelting-molten reduction-oxygen-enriched volatilization", it stably produces a large amount of water-quenched smelting slag. The structure of this type of slag is mainly amorphous phase, and the sensible heat during the cooling process is not effectively utilized. This is a common form of treatment and storage for non-ferrous smelting slag. Example 1

[0046] This embodiment provides an optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag, which specifically includes the following steps: (1) Melt conditioning: When the temperature of the liquid lead-zinc smelting slag is maintained at 1250-1300 °C, conditioning agents CaO, SiO2 and Al2O3 are added and kept at the temperature for 30 min to fully melt and uniformly mix the materials to obtain a conditioning liquid; its composition is: SiO2 49.82 wt%, Al2O3 12.92 wt%, CaO 24.66 wt%, Na2O 5.17 wt%, MgO 4.21 wt%, MnO 3.22 wt%; (2) Annealing: The tempering liquid obtained in step (1) is poured into a graphite mold preheated at 500 °C, and then placed in a muffle furnace and kept at 500 °C for 2 h. After the program is completed, the sample is cooled naturally in the furnace to obtain the mother glass. (3) Crystallization: The parent glass obtained in step (2) is placed in a muffle furnace and heated to 800 °C at a heating rate of 10 °C / min and held for 2 hours. After cooling, microcrystalline glass is obtained.

[0047] The microcrystalline glass prepared above was subjected to performance testing: its density was 2.76 g / cm³. 3 It has a water absorption rate of 0.028%, a compressive strength of 182.07 MPa, a flexural strength of 38.67 MPa, and a Vickers hardness of 744.2 HV.

[0048] Energy consumption calculation for the microcrystalline glass preparation process: mold preheating -1.95 kWh, annealing stage -5 kWh, heating up -1.25 kWh, heat preservation -5 kWh, total energy consumption -13.2 kWh. Example 2

[0049] This embodiment provides an optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag, which specifically includes the following steps: (1) Melt conditioning: When the temperature of the smelting slag is maintained at 1250-1300 °C, the conditioning agents CaO, SiO2 and Al2O3 are added and the temperature is maintained for 30 min to fully melt and uniformly mix the materials to obtain the conditioning liquid; the final chemical composition of the melt is controlled as follows: SiO2 49.82 wt%, Al2O3 12.92 wt%, CaO 24.66 wt%, Na2O 5.17 wt%, MgO 4.21 wt%, MnO 3.22 wt%; (2) Annealing: The tempering liquid obtained in step (1) is poured into a graphite mold preheated at 500 °C, and then placed in a muffle furnace and kept at 500 °C for 2 h. After the program is completed, the sample is cooled naturally in the furnace to obtain the mother glass. (3) Crystallization: The parent glass obtained in step (2) is placed in a muffle furnace and heated to 900 °C at a heating rate of 10 °C / min and held for 2 hours. The resulting microcrystalline glass is then cooled.

[0050] The microcrystalline glass prepared above was subjected to performance testing: its density was 2.79 g / cm³. 3 It has a water absorption rate of 0.021%, a compressive strength of 225.81 MPa, a flexural strength of 46.67 MPa, and a Vickers hardness of approximately 796.8 HV.

[0051] Energy consumption calculation for the microcrystalline glass preparation process: mold preheating -1.95 kWh, annealing stage -5 kWh, heating -1.67 kWh, heat preservation -5 kWh, total energy consumption -13.62 kWh. Example 3

[0052] This embodiment provides an optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag, which specifically includes the following steps: (1) Melt conditioning: When the temperature of the smelting slag is maintained at 1250-1300 °C, the conditioning agents CaO, SiO2, Al2O3 and Fe2O3 are added and kept at the temperature for 30 min to fully melt and uniformly mix the materials to obtain the conditioning liquid; the final chemical composition of the melt is controlled as follows: SiO2 46.83 wt%, Al2O3 12.14 wt%, CaO 23.18 wt%, Na2O 4.86 wt%, MgO 3.96 wt%, MnO 3.03 wt%, Fe2O3 6.00 wt%; (2) Annealing: The tempering liquid obtained in step (1) is poured into a graphite mold preheated at 500 °C, and then placed in a muffle furnace and kept at 500 °C for 2 h. After the program is completed, the sample is cooled naturally in the furnace to obtain the mother glass.

[0053] (3) Crystallization: The parent glass obtained in step (2) is placed in a muffle furnace and heated to 900 °C at a heating rate of 10 °C / min and held for 2 hours. The resulting microcrystalline glass is then cooled.

[0054] The microcrystalline glass prepared above was subjected to performance testing: its density was 2.67 g / cm³. 3 It has a water absorption rate of 0.023%, a compressive strength of 229.11 MPa, a flexural strength of 49.3 MPa, and a Vickers hardness of approximately 902.8 HV.

[0055] Energy consumption calculation for the microcrystalline glass preparation process: mold preheating -1.95 kWh, annealing stage -5 kWh, heating -1.67 kWh, heat preservation -5 kWh, total energy consumption -13.62 kWh. Example 4

[0056] This embodiment provides an optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag, which specifically includes the following steps: (1) Melt conditioning: When the temperature of the smelting slag is maintained at 1250-1300 °C, the conditioning agents CaO, SiO2 and Al2O3 are added and the temperature is maintained for 30 min to allow the materials to melt fully and mix evenly to obtain the conditioning liquid. The final chemical composition of the melt is controlled as follows: SiO2 49.82 wt%, Al2O3 12.92 wt%, CaO 24.66 wt%, Na2O 5.17 wt%, MgO 4.21 wt%, MnO 3.22 wt%.

[0057] (2) Annealing: The tempering liquid obtained in step (1) is poured into a graphite mold preheated at 500 °C, and then placed in a muffle furnace and kept at 500 °C for 2 h. After the program is completed, the sample is cooled naturally in the furnace to obtain the mother glass.

[0058] (3) Crystallization: The parent glass obtained in step (2) is placed in a muffle furnace and heated to 1000 °C at a heating rate of 10 °C / min and held for 2 hours. The resulting microcrystalline glass is then cooled.

[0059] The microcrystalline glass prepared above was subjected to performance testing: its density was 2.81 g / cm³. 3 It has a water absorption rate of 0.01%, a compressive strength of 240.23 MPa, a flexural strength of 47.33 MPa, and a Vickers hardness of approximately 806.8 HV.

[0060] Energy consumption calculation for the microcrystalline glass preparation process: mold preheating -1.95 kWh, annealing stage -5 kWh, heating -2.08 kWh, heat preservation -5 kWh, total energy consumption -14.03 kWh. Example 5

[0061] This embodiment provides an optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag, which specifically includes the following steps: (1) Melt conditioning: When the temperature of the smelting slag is maintained at 1250-1300 °C, the conditioning agents CaO, SiO2, Al2O3 and Fe2O3 are added and the temperature is maintained for 30 min to allow the materials to melt fully and mix evenly to obtain conditioning. The final chemical composition of the melt is controlled as follows: SiO2 46.83 wt%, Al2O3 12.14 wt%, CaO 23.18 wt%, Na2O 4.86 wt%, MgO 3.96 wt%, MnO 3.03 wt%, Fe2O3 6.00 wt%.

[0062] (2) Quenching: Pour the tempering liquid obtained in step (1) into water to obtain amorphous metastable glass quenching slag, dry it in a drying oven at 105°C for 24 h, crush it by ball milling with a ball-to-material ratio of 3:1, and sieve it with an 80-mesh sieve to obtain a parent glass with a particle size ≤178 μm. (3) Sintering: Take 50 g of the parent glass obtained in step (2) and put it into a square crucible and shake it slightly. Then put it into a muffle furnace and heat it to 800 °C at a heating rate of 10 °C / min and hold it for 2 hours. After the program is completed, the sample is naturally cooled to room temperature with the furnace temperature to obtain the microcrystalline glass.

[0063] The microcrystalline glass prepared above was subjected to performance testing: its bulk density was 2.07 g / cm³. 3 It has a water absorption rate of 0.5%, a compressive strength of 62.84 MPa, a flexural strength of 12.64 MPa, and a Vickers hardness of 458.7 HV.

[0064] Energy consumption calculation for the preparation process of microcrystalline glass: Quenching water consumption -100 kg, drying -43.5 kWh, ball milling -1.35 kWh, sintering heating -3.2 kWh, heat preservation -5 kWh, total energy consumption -100 kg water, 53.05 kWh. Example 6

[0065] This embodiment provides an optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag, which specifically includes the following steps: (1) Melt conditioning: When the temperature of the smelting slag is maintained at 1250-1300 °C, conditioning agents CaO, SiO2, Al2O3 and Fe2O3 are added and the temperature is maintained for 30 min to allow the materials to melt fully and mix evenly to obtain conditioning. The final chemical composition of the melt is controlled as follows: SiO2 46.83 wt%, Al2O3 12.14 wt%, CaO 23.18 wt%, Na2O 4.86 wt%, MgO 3.96 wt%, MnO 3.03 wt%, Fe2O3 6.00 wt%; (2) Quenching: Pour the tempering liquid obtained in step (1) into water to obtain amorphous metastable glass quenching slag, dry it in a drying oven at 105°C for 24 h, crush it by ball milling with a ball-to-material ratio of 3:1, and sieve it with an 80-mesh sieve to obtain a parent glass with a particle size ≤178 μm. (3) Sintering: Take 50 g of the parent glass obtained in step (2) and put it into a square crucible and shake it slightly. Then put it into a muffle furnace and heat it to 900 °C at a heating rate of 10 °C / min and hold it for 2 hours. After the program is completed, the sample is naturally cooled to room temperature with the furnace temperature to obtain the microcrystalline glass.

[0066] The microcrystalline glass prepared above was subjected to performance testing: its bulk density was 2.48 g / cm³. 3 It has a water absorption rate of 0.37%, a compressive strength of 88.29 MPa, a flexural strength of 17.82 MPa, and a Vickers hardness of 496.57 HV, with improved overall performance.

[0067] Energy consumption calculation for the preparation process of microcrystalline glass: Quenching water consumption -100 kg, drying -43.5 kWh, ball milling -1.35 kWh, sintering heating -3.63 kWh, heat preservation -5 kWh, total energy consumption -100 kg water, 53.48 kWh. Example 7

[0068] This embodiment provides an optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag, which specifically includes the following steps: (1) Melt conditioning: When the temperature of the smelting slag is maintained at 1250-1300 °C, the conditioning agents CaO, SiO2, Al2O3 and Fe2O3 are added and the temperature is maintained for 30 min to allow the materials to melt fully and mix evenly to obtain conditioning; the final chemical composition of the melt is controlled as follows: SiO2 46.83 wt%, Al2O3 12.14 wt%, CaO 23.18 wt%, Na2O 4.86 wt%, MgO 3.96 wt%, MnO 3.03 wt%, Fe2O3 6.00 wt%; (2) Quenching: Pour the tempering liquid obtained in step (1) into water to obtain amorphous metastable glass quenching slag, dry it in a drying oven at 105°C for 24 h, crush it by ball milling with a ball-to-material ratio of 3:1, and sieve it with an 80-mesh sieve to obtain a parent glass with a particle size ≤178 μm. (3) Sintering: Take 50 g of the parent glass obtained in step (2) and put it into a square crucible and shake it slightly. Then put it into a muffle furnace and heat it to 1000 °C at a heating rate of 10 °C / min and hold it for 2 hours. After the program is completed, the sample is naturally cooled to room temperature with the furnace temperature to obtain the microcrystalline glass.

[0069] The microcrystalline glass prepared above was subjected to performance testing: its bulk density was 2.70 g / cm³. 3 It has a water absorption rate of 0.32%, a compressive strength of 143.29 MPa, a flexural strength of 34.67 MPa, and a Vickers hardness of 528.96 HV. Its overall performance is significantly improved and can meet the basic performance requirements of microcrystalline glass for architectural decoration.

[0070] Energy consumption calculation for the preparation process of microcrystalline glass: Quenching water consumption -100 kg, drying -43.5 kWh, ball milling -1.35 kWh, sintering heating -4.05 kWh, heat preservation -5 kWh, total energy consumption -100 kg water, 53.9 kWh. Example 8

[0071] This embodiment employs an optimized method for directly preparing microcrystalline glass from solid cold smelting slag, specifically including the following steps: (1) High-temperature melting: The composition of the solid cold smelting slag is controlled by adding appropriate amounts of oxides such as CaO, SiO2, Al2O3 and Fe2O3. The material is fully mixed by ball milling. The final chemical composition of the mixture is controlled as follows: SiO2 46.83 wt%, Al2O3 12.14 wt%, CaO 23.18 wt%, Na2O 4.86 wt%, MgO 3.96 wt%, MnO 3.03 wt%, Fe2O3 6.00 wt%. High-temperature melting: 150g of the mixed sample is placed in a crucible and placed in a high-temperature induction furnace. The temperature is raised from room temperature to 1250-1300 °C and maintained for 2 hours to fully melt the liquid melt.

[0072] (2) Quenching: Pour the liquid melt obtained in step (1) into water to obtain amorphous metastable glass quenching slag, dry it in a drying oven at 105 °C for 24 h, crush it by ball milling with a ball-to-material ratio of 3:1, and sieve it with an 80-mesh sieve to obtain the parent glass with a particle size ≤178 μm.

[0073] (3) Sintering: Take 50 g of the parent glass obtained in step (2) and put it into a square crucible and shake it slightly. Then put it into a muffle furnace and heat it to 1000 °C at a heating rate of 10 °C / min and hold it for 2 hours. After the program is completed, the sample is naturally cooled to room temperature with the furnace temperature to obtain the microcrystalline glass.

[0074] The microcrystalline glass prepared above was subjected to performance testing: its bulk density was 2.58 g / cm³. 3 It has a water absorption rate of 0.35%, a compressive strength of 114.27 MPa, a flexural strength of 31.89 MPa, and a Vickers hardness of 436.75 HV.

[0075] Energy consumption calculation for the microcrystalline glass preparation process: high temperature melting - 10.7 kWh, quenching water consumption - 100 kg, drying - 43.5 kWh, ball milling - 1.35 kWh, sintering heating - 4.05 kWh, heat preservation - 5 kWh, total energy consumption - 100 kg water, 64.6 kWh. Example 9

[0076] This embodiment employs an optimized method for directly preparing microcrystalline glass from solid cold smelting slag, specifically including the following steps: (1) High-temperature melting: The composition of the solid cold smelting slag is controlled by adding appropriate amounts of oxides such as CaO, SiO2, Al2O3 and Fe2O3. The material is fully mixed by ball milling. The final chemical composition of the mixture is controlled as follows: SiO2 46.83 wt%, Al2O3 12.14 wt%, CaO 23.18 wt%, Na2O 4.86 wt%, MgO 3.96 wt%, MnO 3.03 wt%, Fe2O3 6.00 wt%. High-temperature melting: 150g of the mixed sample is placed in a crucible and placed in a high-temperature induction furnace. The temperature is raised from room temperature to 1250-1300 °C and maintained for 2 hours to fully melt the liquid melt.

[0077] (2) The liquid melt obtained in step (1) is poured into a graphite mold preheated at 500 °C, and then placed in a muffle furnace and kept at 500 °C for 2 h. After the program is completed, the sample is cooled naturally in the furnace to obtain the mother glass.

[0078] (3) Crystallization: The parent glass obtained in step (2) is placed in a muffle furnace and heated to 1000 °C at a heating rate of 10 °C / min and held for 2 hours. The resulting microcrystalline glass is then cooled.

[0079] The microcrystalline glass prepared above was subjected to performance testing: its bulk density was 2.75 g / cm³. 3It has a water absorption rate of 0.02%, a compressive strength of 236.75 MPa, a flexural strength of 43.75 MPa, and a Vickers hardness of approximately 784.2 HV.

[0080] Energy consumption calculation for the microcrystalline glass preparation process: high temperature melting - 10.7 kWh, mold preheating - 1.95 kWh, annealing stage - 5 kWh, temperature rise - 2.08 kWh, heat preservation - 5 kWh, total energy consumption - 24.73 kWh.

[0081] Figure 2 The XRD patterns of the glass-ceramics prepared by the melt method in Examples 1-4 are shown. The figures show that the glass-ceramics prepared by melt method mainly contain calcium aluminum feldspar, which has a uniform crystal phase distribution, dense structure, and excellent mechanical properties.

[0082] Figure 3 The XRD patterns of the glass-ceramics prepared by the sintering method in Examples 5-7 are shown. The figures show that the glass-ceramics prepared by the sintering method contain calcium aluminum feldspar and iron diopside, and their crystal structure is complex. Compared with the melting method, their mechanical properties are poor.

[0083] Figure 4 The XRD patterns of the microcrystalline glass prepared directly from solid cold smelting slag in Examples 8-9 are shown in the figures. The figures show that although the corresponding crystal phase structure can be obtained by using solid cold smelting slag, its mechanical properties are still reduced and its energy consumption is high.

[0084] In summary, the sintering method can achieve the recrystallization transformation of tempered glass slag, and with increasing temperature, high-performance microcrystalline glass can be obtained. However, its density, crystallization uniformity, and mechanical properties are still lower than those of microcrystalline glass products prepared by the melting method. Meanwhile, solid cold lead-zinc smelting slag was used as a comparative experiment, and the overall energy consumption was calculated. The results of this embodiment further verify the superiority of the optimized process route of the present invention.

[0085] This invention directly utilizes the high-temperature sensible heat of liquid smelting slag for conditioning, completely avoiding the enormous energy consumption of traditional methods that first cool and solidify the slag, then re-crush and remelt it at high temperatures. Example data shows that the total energy consumption of the optimized melting method of this invention (approximately 13.6 kWh) is reduced by about 45% compared to the comparative method of remelting solid cold slag (approximately 24.7 kWh).

[0086] Finally, it should be noted that the terms “comprising,” “including,” or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0087] Although preferred embodiments of the invention have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including both the preferred embodiments and all changes and modifications falling within the scope of the invention.

[0088] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. An optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag, characterized in that, The method includes the following steps: Add a conditioning agent to the liquid lead-zinc smelting slag at a temperature of 1200-1350℃, keep it at the temperature for 30-60 minutes, and melt and mix it evenly to obtain a conditioning solution; The conditioning solution is annealed or quenched to obtain the base glass; The parent glass is transferred to a muffle furnace and heated to a preset temperature at a rate of 10°C / min. It is held at this temperature for 1-4 hours and then allowed to cool naturally to room temperature to obtain microcrystalline glass.

2. The optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag according to claim 1, characterized in that, The conditioning agent includes one or more of SiO2, Al2O3, CaO, and Fe2O3.

3. The optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag according to claim 1, characterized in that, The amount of conditioning agent added is such that the chemical composition of the conditioning solution meets the requirements for preparing microcrystalline glass with calcium aluminum feldspar as the main crystalline phase.

4. The optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag according to claim 1, characterized in that, In the annealing process, the tempering liquid is directly poured into a graphite mold preheated to 500°C and then transferred to a muffle furnace at 500°C for 1-2 hours. The mixture is then allowed to cool naturally to room temperature with the furnace temperature to obtain the mother glass.

5. The optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag according to claim 4, characterized in that, The preset temperature is 800-1000℃, and the performance parameters of the microcrystalline glass include: density ≥2.67 g / cm³. 3 Water absorption ≤0.023%, compressive strength ≥182MPa, flexural strength ≥38 MPa, Vickers hardness ≥744 HV.

6. The optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag according to claim 5, characterized in that, The total energy consumption of microcrystalline glass obtained through annealing is ≤15kWh.

7. The optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag according to claim 1, characterized in that, In the quenching process, the tempering liquid is poured into water for water quenching to obtain amorphous metastable glass quenching slag; the amorphous metastable glass quenching slag is placed in an oven at 105°C and dried for 24 hours to obtain a solid; the solid is ball-milled, crushed, and sieved to obtain the parent glass.

8. The optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag according to claim 7, characterized in that, The ball milling process conditions include: a ball-to-material ratio of 3:1; and a particle size of ≤178μm for the parent glass.

9. The optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag according to claim 8, characterized in that, The preset temperature is 800-1000℃, and the performance parameters of the microcrystalline glass include: bulk density ≥2.07 g / cm³. 3 Water absorption ≤0.5%, compressive strength ≥62.84 MPa, flexural strength ≥12 MPa, Vickers hardness ≥458 HV.

10. The optimized method for directly preparing microcrystalline glass from liquid lead-zinc smelting slag according to claim 9, characterized in that, The total energy consumption of obtaining microcrystalline glass through quenching treatment is ≤54kWh.

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