CN114735936B - Steel slag-based ceramic glaze opacifier and preparation method thereof - Google Patents
Steel slag-based ceramic glaze opacifier and preparation method thereof Download PDFInfo
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- CN114735936B CN114735936B CN202210531693.1A CN202210531693A CN114735936B CN 114735936 B CN114735936 B CN 114735936B CN 202210531693 A CN202210531693 A CN 202210531693A CN 114735936 B CN114735936 B CN 114735936B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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Abstract
A steel slag-based ceramic opacifier and a preparation method thereof are characterized in that steel slag is used as a main raw material, and high bauxite, feldspar, quartz, boric acid, borax and barium carbonate are added as auxiliary raw materials to prepare the ceramic glaze opacifier; slowly heating the steel slag to 1300 ℃ for calcining and removing carbon, ball-milling, mixing, and then removing iron by an iron remover; mixing the calcined steel slag with high bauxite, feldspar, quartz, boric acid, borax and barium carbonate, and crushing by using an air flow mill; roasting the crushed powder to 1250-1350 ℃; then, the roasting product is crushed and finely ground by a ball mill, and the steel slag-based ceramic glaze opacifier is prepared. The steel slag-based ceramic glaze opacifier is added into the transparent base glaze, and the opacified glaze can be prepared after mixing, glazing and sintering, namely the steel slag-based ceramic glaze opacifier is used as an opacifier in place of zirconium silicate, zirconium oxide and the like in the ceramic glaze.
Description
Technical Field
The invention provides a steel slag-based opacifier and a preparation method thereof, belonging to the technical field of high and new technology ceramic material preparation.
Background
Steel slag is a solid waste produced in steelmaking, the new increase of the steel slag per year is about 700 ten thousand tons, but the effective utilization rate is still less than 30 percent. The accumulation of steel slag alone occupies a lot of land and poses a potential threat to the environment. At present, the steel slag is mainly applied to the fields of building materials, glass ceramics and the like. Although the microcrystalline glass can be used for producing products with high added value, the industrialization degree is not high, and the utilization of steel slag is less. The ceramic industry, such as daily ceramic, sanitary ceramic, architectural ceramic and the like, has very large market share and huge yield. Among them, in ceramic glazes, particularly milky glaze, opacifiers are generally used to reduce the light transmittance of the glaze, thereby achieving the decorative effect. At present, the opacifier commonly used in the ceramic industry in China is zirconium silicate, and zirconium dioxide and the like are also used by partial manufacturers. However, zirconium silicate, when used as an opacifying agent, is readily accompanied by radioactivity, which poses a potential threat to the physical health of the user. In addition, zirconium silicate or source minerals thereof in China are mostly imported from Indonesia and Australia, and have high dependence on foreign countries; therefore, the cost of the opacifying agents zirconium silicate and zirconium dioxide is relatively high, greatly influences the market competitiveness and economic benefit of enterprises, and is easily influenced by fluctuations of international markets (price and supply quantity). The technology of the invention takes steel slag as a main raw material and is assisted by other raw materials to prepare the steel slag-based opacifier. The steel slag-based opacifier not only can replace opacifiers such as zirconium silicate and zirconium oxide to eliminate potential radioactive threat, but also can effectively utilize solid waste such as steel slag, realize recycling of the steel slag and reduce dependence on imported zirconium silicate; meanwhile, the production cost of the ceramic glaze can be obviously reduced, and the market competitiveness is improved. In addition, for the steel slag containing more iron, the related enterprises have the capability of extracting iron from the steel slag, so that the iron content in the steel slag is greatly reduced, and good raw material conditions are provided for preparing the ceramic glaze opacifier.
Disclosure of Invention
The invention mainly solves the problems of low utilization rate of steel slag, high cost of zirconium silicate opacifier, potential radioactivity threat and the like, and provides a solution for efficiently utilizing the steel slag and realizing the recycling of the steel slag, namely a method for preparing a ceramic opacifier by using the steel slag as a main raw material. The invention provides a steel slag-based ceramic glaze opacifier with high efficiency, safety, reliability, easy operation and low cost and a preparation method thereof, and the technical scheme is as follows:
1. the preparation method of the steel slag-based ceramic opacifier is characterized by comprising the following steps: (1) Preparing a ceramic glaze opacifier by taking steel slag with iron content lower than 1wt% and granularity smaller than 300 meshes in the market as a main raw material and taking bauxite, feldspar, quartz, boric acid, borax, barium carbonate and the like as auxiliary raw materials; the primary chemical components of the steel slag after preliminary iron removal are as follows: caO: 51-57 wt% of SiO 2 ：17~23 wt%，Al 2 O 3 ：7~9 wt%，MgO：7~10 wt%， Fe 2 O 3 Less than 2.2 and wt percent, the other steps are as follows: 2-3.5%, burn loss rate: 2-3.6%.
A steel slag-based ceramic opacifier and a preparation method thereof are characterized in that the steel slag in the step (1) refers to converter steel slag, and can also refer to open-hearth steel slag and electric furnace steel slag.
(2) A steel slag-based ceramic opacifier and a preparation method thereof are characterized in that: in an oxidizing atmosphere, slowly heating the steel slag in the step (1) to 1150-1300 ℃, and then preserving heat for 4-8 hours to fully oxidize the reducing substances in the steel slag and completely remove combustible substances including carbon; naturally cooling to room temperature, ball-milling and mixing water and steel slag according to the mass ratio of 1:1, then removing iron by using an iron remover, and controlling the content of ferric oxide in the steel slag to be not higher than 0.2 wt percent after removing iron.
A steel slag-based ceramic opacifier and a preparation method thereof are characterized in that: the oxidizing atmosphere in the step (2) means that the residual volume fraction of oxygen in the combustion atmosphere is 0.2-0.5%.
A steel slag-based ceramic opacifier and a preparation method thereof are characterized in that: the slow heating in the step (2) means that the heating temperature rising speed is 0.1-1 ℃/min so as to avoid burning.
(3) A steel slag-based ceramic opacifier and a preparation method thereof are characterized in that: mixing the steel slag treated and dried in the step (2) with high bauxite, feldspar, quartz, boric acid, borax and barium carbonate, and grinding the mixture into powder with the granularity of 900-1200 meshes by using an air flow mill.
A steel slag-based ceramic opacifier and a preparation method thereof are characterized in that: the addition amount of the various additive raw materials in the steel slag in the step (3) is as follows: the addition of the high bauxite is 2-5 wt% of steel slag, the addition of the feldspar is 1-2 wt% of steel slag, the addition of the quartz is 2-3 wt% of steel slag, the addition of the boric acid is 1-2 wt% of steel slag, the addition of the borax is 2-3 wt% of steel slag, and the addition of the barium carbonate is 1-2 wt% of steel slag; the addition amount of each of the additive materials includes, but is not limited to, the above range, and is adjusted within ±50% according to the fluctuation of the chemical composition of the steel slag.
(4) A steel slag-based ceramic opacifier and a preparation method thereof are characterized in that: and (3) heating the mixed powder in the step (3) to 1250-1350 ℃ in a tunnel kiln, and preserving heat for 2-4 hours for roasting. And (3) crushing the roasted product by using a ball mill, and finely grinding the crushed product to 200-500 meshes to obtain the steel slag-based ceramic glaze opacifier.
(5) A steel slag-based ceramic opacifier and a preparation method thereof are characterized in that: the steel slag-based ceramic glaze opacifier in the step (4) is added into transparent base glaze, and the transparent base glaze is prepared into an opacified glaze after mixing, glazing and sintering, namely, the steel slag-based ceramic glaze opacifier can replace opacifiers such as zirconium silicate, zirconium oxide and the like to be used in the ceramic industry.
A steel slag-based ceramic opacifier and a preparation method thereof are characterized in that: the basic glaze in the step (5) refers to building ceramic basic glaze, and also can refer to sanitary ceramic basic glaze or daily ceramic basic glaze.
Detailed Description
Example 1
The primary iron-removing treated steel slag purchased from the market has the granularity of 500 meshes and the chemical composition (wt%) as follows: siO (SiO) 2 ：20.7 %，Al 2 O 3 ：7.4 %，MgO：7.9 %，CaO：56.3%，Fe 2 O 3 1.6 percent of the components, the others: 3.0 Percent loss on ignition: 3.1%; heating the steel slag to 1300 ℃ at a speed of 0.5 ℃/min by using a batch kiln in an oxidizing atmosphere (the excess volume fraction of oxygen is 0.5%), and then preserving the heat for 4 hours to fully oxidize the reducing substances in the steel slag and completely remove combustible substances including carbon; naturally cooling to room temperature, ball-milling and mixing water and steel slag according to the mass ratio of 1:1, and then removing iron by using an iron remover, wherein the content of iron oxide in the steel slag after iron removal is 0.1 wt%; mixing the dried steel slag with high bauxite, feldspar, quartz, boric acid, borax and barium carbonate, and crushing the mixture into powder with the granularity of 900 meshes by using an air flow mill; the addition amount of each additive in the steel slag is as follows: the addition amount of the high bauxite is 2wt percent, the addition amount of the feldspar is 1wt percent, the addition amount of the quartz is 2 weight percent, the addition amount of the boric acid is 2wt percent, the addition amount of the borax is 3 wt percent, and the addition amount of the barium carbonate is 2wt percent; the mixed powder is heated to 1250 ℃ in a tunnel kiln and is kept warm for 3 hours for roasting. And (3) crushing the roasted product by using a ball mill, and finely grinding the crushed product to 350 meshes to obtain the steel slag-based ceramic glaze opacifier. The steel slag-based ceramic glaze opacifier is added into the transparent basic glaze of the building ceramic, and the opacified glaze can be prepared after mixing, glazing and firing, namely, the steel slag-based ceramic glaze opacifier can be used in the building ceramic industry instead of opacifiers such as zirconium silicate.
Example 2
Primary iron removal treatment from marketThe granularity of the steel slag is 600 meshes, and the chemical composition (wt%) is: siO (SiO) 2 ：19.8，Al 2 O 3 ：7.9，MgO：8.6，CaO：55.1，Fe 2 O 3 2.1, the others: 3.3, loss on ignition: 3.2. heating the steel slag to 1200 ℃ at a speed of 1 ℃/min by using a batch kiln in an oxidizing atmosphere (the excess volume fraction of oxygen is 0.2%), and then preserving the heat for 6 hours to fully oxidize the reducing substances in the steel slag and completely remove the combustible substances including carbon; naturally cooling to room temperature, ball-milling and mixing water and steel slag according to the mass ratio of 1:1, and then removing iron by using an iron remover, wherein the content of iron oxide in the steel slag after iron removal is 0.1 wt%; mixing the dried steel slag with high bauxite, feldspar, quartz, boric acid, borax and barium carbonate, and crushing the mixture into powder with the granularity of 1000 meshes by using an air flow mill; the addition amount of each additive in the steel slag is as follows: the addition amount of the high bauxite is 3 wt percent, the addition amount of the feldspar is 2wt percent, the addition amount of the quartz is 3 wt percent, the addition amount of the boric acid is 1wt percent, the addition amount of the borax is 2wt percent, and the addition amount of the barium carbonate is 1wt percent; the mixed powder is heated to 1300 ℃ in a tunnel kiln and is kept warm for 4 hours for roasting. The product prepared by roasting is crushed by a ball mill and finely ground to 500 meshes, and the steel slag-based ceramic glaze opacifier is prepared. The steel slag-based ceramic glaze opacifier is added into the transparent base glaze of the daily ceramic, and the opacified glaze can be prepared after mixing, glazing and firing, namely, the steel slag-based ceramic glaze opacifier can replace opacifiers such as zirconium silicate and the like to be used in the daily ceramic industry.
Example 3
The primary iron-removing treated steel slag purchased from the market has the granularity of 800 meshes and the chemical composition (wt%) as follows: siO (SiO) 2 ：19.9，Al 2 O 3 ：7.9，MgO：8.2，CaO：56.2，Fe 2 O 3 1.9, the others are 3.1, loss on ignition: 2.8; heating the steel slag to 1150 ℃ at a speed of 0.6 ℃/min in an oxidizing atmosphere (the excess volume fraction of oxygen is 0.3%) by using a batch kiln, and then preserving heat for 8 hours to fully oxidize the reducing substances in the steel slag and completely remove combustible substances including carbon; naturally cooling to room temperature, ball milling and mixing water and steel slag according to the mass ratio of 1:1Mixing, then removing iron by an iron remover, wherein the content of iron oxide in the steel slag after iron removal is 0.19 and wt percent; mixing the dried steel slag with high bauxite, feldspar, quartz, boric acid, borax and barium carbonate, and crushing the mixture into powder with the granularity of 1000 meshes by using an air flow mill; the addition amount of each additive in the steel slag is as follows: the addition amount of the high bauxite is 3.8 wt percent, the addition amount of the feldspar is 2wt percent, the addition amount of the quartz is 2.5 wt percent, the addition amount of the boric acid is 1wt percent, the addition amount of the borax is 2wt percent, and the addition amount of the barium carbonate is 1wt percent; heating the mixed powder to 1350 ℃ in a tunnel kiln, and preserving heat for 3 hours to bake. And (3) crushing the roasted product by using a ball mill, and finely grinding the crushed product to 300 meshes to obtain the steel slag-based ceramic glaze opacifier. The steel slag-based ceramic glaze opacifier is added into transparent basic glaze of sanitary ceramic, and after mixing, glazing and sintering, the opacified glaze can be prepared, namely, the steel slag-based ceramic glaze opacifier can replace opacifiers such as zirconium silicate, zirconium oxide and the like to be used in the sanitary ceramic industry.
Claims (3)
1. The steel slag-based ceramic opacifier is characterized in that steel slag with the granularity smaller than 300 meshes is used as a main raw material, and bauxite, feldspar, quartz, boric acid, borax and barium carbonate are added as auxiliary raw materials to prepare the ceramic glaze opacifier; the main chemical components of the steel slag are as follows: caO: 51-57 wt% of SiO 2 ：17~23 wt%，Al 2 O 3 ：7~9 wt%，MgO：7~10 wt%， Fe 2 O 3 Less than 2.2 and wt percent, the other steps are as follows: 2-3.5 wt%, burn loss rate: 2-3.6. 3.6 wt%; in an intermittent kiln, controlling the atmosphere to be an oxidizing atmosphere, slowly heating steel slag to 1150-1300 ℃ for calcination and carbon removal, preserving heat for 4-8 hours, naturally cooling to room temperature, ball-milling and mixing water and steel slag according to the mass ratio of 1:1, then removing iron by using an iron remover, and controlling the content of ferric oxide in the steel slag to be not higher than 0.2 wt% after iron removal; mixing calcined steel slag with high bauxite, feldspar, quartz, boric acid, borax and barium carbonate, wherein the addition amount of the high bauxite is 2-5 wt% of the steel slag, the addition amount of the feldspar is 1-2 wt% of the steel slag, the addition amount of the quartz is 2-3 wt% of the steel slag, the addition amount of the boric acid is 1-2 wt% of the steel slag, and the addition amount of the borax is 2-3 wt% of the steel slag; then using air flowGrinding to powder with the granularity of 900-1200 meshes; heating the mixed and crushed powder to 1250-1350 ℃ in a tunnel kiln, and preserving heat for 2-4 hours for roasting; and then, crushing the roasting product by using a ball mill, and finely grinding the crushed roasting product to 200-500 meshes to prepare the steel slag-based ceramic glaze opacifier.
2. The steel slag based ceramic opacifier of claim 1, wherein the steel slag based ceramic glaze opacifier is added into transparent base glaze, and the opacified glaze is prepared after mixing, glazing and firing.
3. The steel slag based ceramic opacifier of claim 2, wherein the transparent base glaze is a building ceramic base glaze, a household ceramic base glaze or a sanitary ceramic base glaze.
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| CN102557755A (en) * | 2011-12-14 | 2012-07-11 | 谢健城 | Opacified glaze containing lithium oxide |
| CN105924216A (en) * | 2016-05-04 | 2016-09-07 | 山东理工大学 | Method for preparing lightweight porous aluminum phosphate-zirconium silicate ceramic balls |
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| CN106277781A (en) * | 2015-05-29 | 2017-01-04 | 宝山钢铁股份有限公司 | Utilize the method that high-temperature liquid state industrial slag produces pottery glaze |
| US20190031568A1 (en) * | 2016-02-19 | 2019-01-31 | «NIKA-PETROTECH» Limited Liability Company | Ceramic proppant and method for producing same |
| CN109761583A (en) * | 2019-03-29 | 2019-05-17 | 重庆唯美陶瓷有限公司 | Black ink-jet throws glaze Ceramic Tiles and preparation method thereof entirely |
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- 2022-05-17 CN CN202210531693.1A patent/CN114735936B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054410A (en) * | 1991-03-08 | 1991-09-11 | 重庆市硅酸盐研究所 | Prescription with making porcelain glaze with Ti-containing slag |
| CN1962519A (en) * | 2006-12-04 | 2007-05-16 | 武汉共达玻璃钢工程技术有限公司 | Pavement colored sand and its preparation |
| CN102557755A (en) * | 2011-12-14 | 2012-07-11 | 谢健城 | Opacified glaze containing lithium oxide |
| CN106277789A (en) * | 2015-05-29 | 2017-01-04 | 宝山钢铁股份有限公司 | A kind of method utilizing steel slag preparation pottery glaze |
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| US20190031568A1 (en) * | 2016-02-19 | 2019-01-31 | «NIKA-PETROTECH» Limited Liability Company | Ceramic proppant and method for producing same |
| CN105924216A (en) * | 2016-05-04 | 2016-09-07 | 山东理工大学 | Method for preparing lightweight porous aluminum phosphate-zirconium silicate ceramic balls |
| CN109761583A (en) * | 2019-03-29 | 2019-05-17 | 重庆唯美陶瓷有限公司 | Black ink-jet throws glaze Ceramic Tiles and preparation method thereof entirely |
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