阅读说明：本技术 一种铁尾矿基高性能多孔微晶玻璃及其制备方法 (Iron tailing based high-performance porous glass ceramic and preparation method thereof ) 是由 胡国峰 邵雁 郭华军 刘颖 刘子豪 向浩 蒋庆肯 许晓明 姜明明 于 2020-11-30 设计创作，主要内容包括：本发明提供了一种铁尾矿基高性能多孔微晶玻璃及其制备方法,多孔微晶玻璃主要成分的重量组分为：铁尾矿粉30％-70％、助熔剂10％-20％、成核剂5％-15％、发泡剂10％-20％、粘结剂5％-15％；制备方法采用步骤：称重、研磨、熔制和水淬、收集玻璃珠粉磨成粉、混合各助剂原料进行压制成型、核化和晶化、随炉冷却。本发明以铁尾矿为原料,制备条件较温和,合成工艺简单,成本低,易于大规模生产,对铁尾矿资源进行了合理化利用,制备得到的多孔微晶玻璃具有密度小、质量轻、比表面积大、阻尼性能好等优异的性能,可以广泛应用于在建筑、环保、能源、化学工业。(The invention provides iron tailing based high-performance porous glass ceramics and a preparation method thereof, wherein the porous glass ceramics mainly comprises the following components in parts by weight: 30-70% of iron tailing powder, 10-20% of fluxing agent, 5-15% of nucleating agent, 10-20% of foaming agent and 5-15% of binder; the preparation method comprises the following steps: weighing, grinding, melting and water quenching, collecting glass bead powder, grinding into powder, mixing all auxiliary raw materials, performing compression molding, nucleating and crystallizing, and cooling along with a furnace. The invention takes the iron tailings as raw materials, has mild preparation conditions, simple synthesis process, low cost and easy large-scale production, reasonably utilizes iron tailing resources, and the prepared porous glass ceramics have excellent performances of small density, light weight, large specific surface area, good damping performance and the like, and can be widely applied to the building, environmental protection, energy and chemical industries.)

1. The iron tailing based high-performance porous glass ceramics is characterized by comprising the following main components in parts by weight: 30-70% of iron tailing powder, 10-20% of fluxing agent, 5-15% of nucleating agent, 10-20% of foaming agent and 5-15% of binder.

2. The iron tailing based high-performance porous glass-ceramic according to claim 1, characterized in that: the fluxing agent comprises one or a combination of more of feldspar, soda ash, boric acid, lead compounds and barium compounds.

3. The iron tailing based high-performance porous glass-ceramic according to claim 1, characterized in that: the adhesive comprises one or a combination of several of polyethylene glycol, alpha-cyanoacrylate and polymeric cyclic ether derivatives.

4. The iron tailing based high-performance porous glass-ceramic according to claim 1, characterized in that: the nucleating agent comprises V₂O₅，Cr₂O₃、TiO₂One or a combination of several of them.

5. The iron tailing based high-performance porous glass-ceramic according to claim 1, characterized in that: the foaming agent comprises NaN₃、CaCO₃、Na₂CO₃、BaCO₃One or a combination of several of them.

6. The method for preparing the iron tailing based high-performance porous glass ceramics according to any one of claims 1 to 5, which is characterized by comprising the following steps:

s1, weighing iron tailing powder, fluxing agent, nucleating agent, foaming agent and binder according to the proportion set by the formula;

s2, fully grinding the iron tailing powder, and uniformly mixing;

s3, melting the powder ground in the step S2 into molten glass, pouring the molten glass into water, quenching and quenching;

s4, collecting the water-quenched glass particles, drying and grinding to obtain glass powder for later use;

s5, mixing the glass powder, the fluxing agent, the nucleating agent, the foaming agent and the binder, adding water, stirring uniformly, and putting into a die for compression molding;

s6, forming, naturally drying, sintering, nucleating and crystallizing, and cooling with the furnace to obtain the porous glass ceramics.

7. The method for preparing the iron tailing based high-performance porous glass ceramics according to claim 6, which is characterized in that: step S3 is specifically that the uniformly mixed powder is placed in a 30mL corundum crucible, placed in a box-type resistance furnace, heated to 1250 ℃ at the heating rate of 4 ℃/min, and kept for 3h, and then the molten and clarified glass liquid is poured into water of 20 ℃ for water quenching and rapid cooling.

8. The method for preparing the iron tailing based high-performance porous glass ceramics according to claim 6, which is characterized in that: step S5 is to press and mold a cylindrical mold with a diameter of 30mm and a depth of 5mm under a pressure of 20-25 MPa.

9. The method for preparing the iron tailing based high-performance porous glass ceramics according to claim 6, which is characterized in that: in the sintering process of the step S6, the temperature is kept for 50min to 70min at 800 ℃ by adopting the temperature rise rate of 5 ℃/min before 800 ℃, then the temperature is raised by adopting the temperature rise rate of 6 ℃/min, and the temperature is kept for 45min to 60min at 1000 ℃.

Technical Field

The invention belongs to the technical field of environmental protection, and particularly relates to iron tailing based high-performance porous glass ceramics and a preparation method thereof.

Background

The iron tailings are group mining waste materials formed by naturally dehydrating tailing slurry discharged by a concentrating mill in iron ore development. The discharge amount of iron tailings of mines in China is large, the direct land pollution area caused by the iron tailings is hundreds of thousands of hectares, the indirect land pollution area reaches millions of hectares, and the increase trend is shown. Because the utilization research of the iron tailings in China starts late, the components and the properties of the iron tailings are not comprehensively known, the environment-friendly consciousness is poor, the utilization of the tailings is not paid attention to, and the utilization rate of the iron tailings in China is extremely low.

The foam glass is invented by the United states of petzburg Corning company, and is produced in small batches in China since the middle of the 70 th 20 th century, the product varieties are products such as sound-absorbing foam glass, building heat-insulating foam glass, low-borosilicate foam glass, high-borosilicate foam glass, neutral foam glass, foam glass for cleaning, colored foam glass and the like are gradually developed from single heat-insulating foam glass, and the products are produced by industrial waste residues to produce foam glass raw materials such as waste glass, fly ash, volcanic ash and the like, can effectively reduce the production cost, are beneficial to environmental protection and are widely adopted. Therefore, the application range of the porous glass ceramic is limited, most of the porous glass ceramic is used in the fields of chemical industry, electric power, refrigeration and the like, and is used as a few of decoration and wall materials.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides the iron tailing based high-performance porous glass ceramics and the preparation method thereof, which not only realize the resource utilization of the iron tailings, but also solve the problems of complex production process, high cost, low mechanical strength, poor thermal shock resistance and the like in the prior art.

The invention is realized by the following steps:

the invention provides iron tailing based high-performance porous glass ceramics which mainly comprise the following components in parts by weight: 30-70% of iron tailing powder, 10-20% of fluxing agent, 5-15% of nucleating agent, 10-20% of foaming agent and 5-15% of binder.

The iron tailing powder mainly comprises quartz and hematite and can be a cheap raw material for preparing microcrystalline glass taking barium ferrite as a main crystal phase; the functional glass ceramics is prepared by taking the iron tailings as the main component, so that the raw material cost of the barium ferrite glass ceramics can be reduced, the added value of iron ore materials is improved, and the environmental protection is facilitated.

Further, the fluxing agent comprises one or a combination of more of feldspar, soda ash, boric acid, lead compounds and barium compounds; the fluxing agent mainly plays the roles of fluxing and stabilizing agent in the glass, and the chemical stability and the mechanical strength of the glass are improved.

Further, the binder comprises one or a combination of several of polyethylene glycol, a-cyanoacrylate and polymeric cyclic ether derivatives; the adhesive ensures the bonding strength between the abrasive and the matrix, and can effectively improve the strength of the pressed blank or prevent powder segregation.

Further, the nucleating agent comprises V₂O₅，Cr₂O₃、TiO₂One or a combination of several of (a); the nucleating agent provides required crystal nucleus in a molten state, so that the polymer is converted from original homogeneous nucleation to heterogeneous nucleation, the crystallization speed is accelerated, the crystal grain structure is refined, the rigidity of the product is improved, the forming period is shortened, the size stability of the final product is maintained, and the transparency, the surface gloss and the physical and mechanical properties of the polymer are improved.

Further, the blowing agent comprises NaN₃、CaCO₃、Na₂CO₃、BaCO₃One or a combination of several of (a); the foaming agent can release gases such as carbon dioxide or nitrogen after being heated and decomposed to form pores in the glass body; the foaming agent has higher surface activity, can effectively reduce the surface tension of liquid, is arranged on the surface of a liquid film by two electron layers to surround air to form bubbles, and then forms foam by single bubbles.

The invention also provides a preparation method of the iron tailing based high-performance porous glass ceramics, which comprises the following steps:

s1, weighing iron tailing powder, fluxing agent, nucleating agent, foaming agent and binder according to the proportion set by the formula;

s2, fully grinding the iron tailing powder, and uniformly mixing;

s3, melting the powder ground in the step S2 into molten glass, pouring the molten glass into water, quenching and quenching;

s4, collecting the water-quenched glass particles, drying and grinding to obtain glass powder for later use;

s5, mixing the glass powder, the fluxing agent, the nucleating agent, the foaming agent and the binder, adding water, stirring uniformly, and putting into a die for compression molding;

s6, forming, naturally drying, sintering, nucleating and crystallizing, and cooling with the furnace to obtain the porous glass ceramics.

Further, step S3 specifically includes placing the uniformly mixed powder in a 30mL corundum crucible, placing the corundum crucible in a box-type resistance furnace, raising the temperature to 1250 ℃ at a heating rate of 4 ℃/min, preserving the temperature for 3h, and pouring the molten and clarified glass liquid into water at 20 ℃ for water quenching and quenching.

Further, the step S5 is to press-mold a cylindrical mold with a diameter of 30mm and a depth of 5mm under a pressure of 20-25 MPa.

Further, in the sintering process of step S6, the temperature is kept at 800 ℃ for 50-70 min at a temperature rise rate of 5 ℃/min before 800 ℃, then the temperature is raised at a temperature rise rate of 6 ℃/min, and the temperature is kept at 1000 ℃ for 45-60 min.

The invention has the following beneficial effects:

1. the method takes the iron tailings as raw materials, has mild preparation conditions, simple synthesis process, low cost and easy large-scale production, and reasonably utilizes iron tailing resources.

2. The porous glass ceramics prepared by the invention has the excellent performances of small density, light weight, large specific surface area, good damping performance and the like, and can be widely applied to the building, environmental protection, energy and chemical industries.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

In this embodiment, the porous glass ceramics is prepared by using 30% of iron tailings powder, 20% of fluxing agent, 15% of nucleating agent, 20% of foaming agent and 15% of binder, wherein the fluxing agent is boric acid, and the nucleating agent is V₂O₅And Cr₂O₃Mixing in equal proportion, and using NaN as foaming agent₃And CaCO₃Mixing at equal ratio, and mixing with polyethylene glycol as binder.

The high-performance porous microcrystalline glass based on the iron tailings is prepared according to the following steps:

s1, weighing iron tailing powder, a fluxing agent, a nucleating agent, a foaming agent and a binder according to a set proportion;

s2, pouring the iron tailing powder into a mortar, and fully grinding to uniformly mix the iron tailing powder and reduce particles;

s3, placing the uniformly mixed powder into a 30mL corundum crucible, placing the corundum crucible into a box-type resistance furnace, raising the temperature to 1250 ℃ at a heating rate of 4 ℃/min, preserving the temperature for 3 hours, and pouring the molten and clarified glass liquid into water at 20 ℃ for water quenching and quenching;

s4, collecting the water-quenched glass particles, naturally drying, and grinding by using a ball mill to obtain glass powder for later use;

s5, mixing glass powder, fluxing agent, nucleating agent, foaming agent and binder. Putting into a crucible, adding a certain amount of water, stirring uniformly, putting into a cylindrical mold with the diameter of 30mm and the depth of 5mm, and pressing and molding under the pressure of 20-25 MPa;

and S6, placing the formed glass into a natural environment for natural drying for one day and night, then placing the glass into a 50mL corundum crucible for heating, nucleating and crystallizing, wherein in the sintering process, the temperature is raised at the temperature of 800 ℃ by adopting the temperature raising rate of 5 ℃/min, the temperature is kept at 800 ℃ for 50min, the temperature is raised at the temperature raising rate of 6 ℃/min, the temperature is kept at 1000 ℃ for 45min, and then the glass is cooled along with a furnace to obtain the porous glass ceramics.

Example 2

In this embodiment, the porous glass ceramics is prepared by using 55% of iron tailings powder, 15% of fluxing agent, 8% of nucleating agent, 12% of foaming agent and 10% of binder, wherein the fluxing agent is barium compound, and the nucleating agent is V₂O₅And Cr₂O₃Mixing in equal proportion, and using NaN as foaming agent₃And CaCO₃Mixing at equal ratio, and mixing with polyethylene glycol as binder.

The high-performance porous microcrystalline glass based on the iron tailings is prepared according to the following steps:

s1, weighing iron tailing powder, a fluxing agent, a nucleating agent, a foaming agent and a binder according to a set proportion;

s2, pouring the iron tailing powder into a mortar, and fully grinding to uniformly mix the iron tailing powder and reduce particles;

s3, placing the uniformly mixed powder into a 30mL corundum crucible, placing the corundum crucible into a box-type resistance furnace, raising the temperature to 1250 ℃ at a heating rate of 4 ℃/min, preserving the temperature for 3 hours, and pouring the molten and clarified glass liquid into water at 20 ℃ for water quenching and quenching;

s4, collecting the water-quenched glass particles, naturally drying, and grinding by using a ball mill to obtain glass powder for later use;

s5, mixing glass powder, fluxing agent, nucleating agent, foaming agent and binder. Putting into a crucible, adding a certain amount of water, stirring uniformly, putting into a cylindrical mold with the diameter of 30mm and the depth of 5mm, and pressing and molding under the pressure of 20-25 MPa;

and S6, placing the formed glass into a natural environment for natural drying for one day and night, then placing the glass into a 50mL corundum crucible for heating, nucleating and crystallizing, wherein in the sintering process, the temperature is raised at the temperature of 800 ℃ by adopting the temperature raising rate of 5 ℃/min, the temperature is maintained at 800 ℃ for 60min, the temperature is raised at the temperature raising rate of 6 ℃/min, the temperature is maintained at 1000 ℃ for 50min, and then the glass is cooled along with a furnace to obtain the porous glass ceramics.

Example 3

In this embodiment, the porous glass ceramics is prepared by using 70% of iron tailings powder, 5% of fluxing agent, 10% of nucleating agent, 10% of foaming agent and 5% of binder, wherein the fluxing agent is feldspar, and the nucleating agent is TiO₂The foaming agent is NaN₃、CaCO₃And BaCO₃Mixing in equal proportion, and the adhesive is alpha-cyanoacrylate.

The high-performance porous microcrystalline glass based on the iron tailings is prepared according to the following steps:

s1, weighing iron tailing powder, a fluxing agent, a nucleating agent, a foaming agent and a binder according to a set proportion;

s2, pouring the iron tailing powder into a mortar, and fully grinding to uniformly mix the iron tailing powder and reduce particles;

s3, placing the uniformly mixed powder into a 30mL corundum crucible, placing the corundum crucible into a box-type resistance furnace, raising the temperature to 1250 ℃ at a heating rate of 4 ℃/min, preserving the temperature for 3 hours, and pouring the molten and clarified glass liquid into water at 20 ℃ for water quenching and quenching;

s4, collecting the water-quenched glass particles, naturally drying, and grinding by using a ball mill to obtain glass powder for later use;

s5, mixing glass powder, fluxing agent, nucleating agent, foaming agent and binder. Putting into a crucible, adding a certain amount of water, stirring uniformly, putting into a cylindrical mold with the diameter of 30mm and the depth of 5mm, and pressing and molding under the pressure of 20-25 MPa;

s6, placing the formed glass into a natural environment for natural drying for a day and a night, then placing the glass into a 50mL corundum crucible for heating, nucleating and crystallizing, wherein in the sintering process, the temperature is raised at the temperature of 800 ℃ by adopting the temperature raising rate of 5 ℃/min, the temperature is maintained at 800 ℃ for 70min, the temperature is raised at the temperature raising rate of 6 ℃/min, the temperature is maintained at 1000 ℃ for 60min, and then the glass is cooled along with a furnace to obtain the porous glass ceramics.

The porous glass ceramics obtained in example 1, example 2 and example 3 were subjected to performance tests, and the results are shown in table 1.

TABLE 1

As can be seen from Table 1, the porous microporous glass prepared by the invention has the characteristics of good compressive strength, good heat conductivity, high strength and strong thermal shock resistance under the condition of high porosity; the invention takes the iron tailings as raw materials, has mild preparation conditions, simple synthesis process, low cost and easy large-scale production, reasonably utilizes iron tailing resources, and the prepared porous microporous glass has light weight, high strength and strong thermal shock resistance and can be widely applied to the building, environmental protection, energy and chemical industries.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.