CN109626833B - Method for preparing continuous basalt fibers from blast furnace slag - Google Patents
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- CN109626833B CN109626833B CN201811115337.1A CN201811115337A CN109626833B CN 109626833 B CN109626833 B CN 109626833B CN 201811115337 A CN201811115337 A CN 201811115337A CN 109626833 B CN109626833 B CN 109626833B
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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
- C03C13/00—Fibre or filament compositions
- C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
- C03B37/022—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor from molten glass in which the resultant product consists of different sorts of glass or is characterised by shape, e.g. hollow fibres, undulated fibres, fibres presenting a rough surface
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
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Abstract
The invention discloses a method for preparing continuous basalt fiber by using blast furnace slag, which takes industrial solid waste blast furnace slag, fly ash and coal gangue as main raw materials, then adds quartz sand, zirconia, cerium oxide and titanium tailings, reasonably mixes the contents of all components, then ball-mills the mixture by a ball mill to uniformly mix all components, then carries out melting reaction on the mixed material at a proper high temperature, and finally carries out wire drawing by a platinum-rhodium alloy bushing plate to obtain the continuous basalt fiber. The invention properly improves CaO and TiO2And ZrO2In an amount such that the basalt fiber forms SiO2‑Al2O3‑CaO‑MgO‑TiO2‑ZrO2The system reduces the high-temperature viscosity of the molten liquid, and obviously increases the strength, thermal stability and corrosion resistance of the glass; the purpose of comprehensively utilizing industrial solid wastes is realized.
Description
Technical Field
The invention relates to the field of inorganic fiber preparation, in particular to a method for preparing continuous basalt fibers by using blast furnace slag.
Background
The Continuous Basalt fiber (CBF or BF for short) is an environment-friendly inorganic fiber material, has excellent performances of light weight, high strength, high temperature resistance, corrosion resistance, oxidation resistance, radiation protection, heat insulation, sound insulation and the like, and has wide application in the fields of aerospace, automobiles, ships, civil engineering traffic, energy environment, chemical fire protection, national defense and military industry and the like. Especially in the building field, the cement-based material is used as a novel cement reinforcing material to partially replace reinforcing steel bars, has good compatibility with cement and concrete, and can effectively enhance the strength and the crack resistance of the cement-based material.
Currently, raw materials for preparing basalt fibers are mainly used for exploiting natural basalt, and researches on raw materials for preparing basalt fibers are few. Natural basalt, which is used to prepare basalt fiber, has main components as shown in table 1.
TABLE 1 Natural basalt Components used to prepare basalt fibers
| Composition (I) | SiO2 | Al2O3 | Fe2O3+FeO | CaO | MgO+MnO | TiO2 | Others |
| Content/% | 45～55 | 12～18 | 4.5～14 | 5～12 | 3.0～7.0 | 0.9～2.0 | 2.0～3.5 |
The blast furnace slag is prepared from gangue in ore, ash in fuel and non-volatile component in flux during iron makingAnd other impurities which cannot enter the pig iron. Generally, when the grade of the charging material reaches 60-66%, 250-350 kg of slag can be produced for each 1 ton of pig iron. Calculated by 8 tons of iron produced in China per year, the production amount of blast furnace slag per year reaches more than 2.4 hundred million tons, and the proportion of the blast furnace slag in all industrial waste residue discharge amount is nearly one third. The total utilization rate of the blast furnace slag in China is low and is not as high as 50% of the total amount of the blast furnace slag, and a large amount of blast furnace slag is accumulated to cause great pressure on the ecological environment. The main component of the blast furnace slag is SiO2、CaO、 Al2O3、Fe2O3MnO, MgO and the like are similar to the components of basalt, so that the content of main components corresponding to the basalt can be achieved by adding related raw materials, and the resource recycling of the blast furnace slag is realized.
Disclosure of Invention
The invention aims to provide a method for preparing continuous basalt fibers by using blast furnace slag as a main raw material so as to realize resource recycling of industrial waste blast furnace slag.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the method for preparing the continuous basalt fiber by using the blast furnace slag is characterized in that the continuous basalt fiber comprises the following components in percentage by weight: 20-40 parts of blast furnace slag, 25-35 parts of coal gangue, 31-46 parts of fly ash, 10-23 parts of quartz sand, 2.5-4.3 parts of zirconia, 2.1-2.9 parts of cerium oxide and 10-19 parts of titanium tailings.
The blast furnace slag comprises the following components in percentage by weight: SiO22 35～48％，Al2O3 7～18％，Fe2O30.1～0.7％， CaO29～46％，MgO 4～13％，K2O and Na2O1.1～2.5％。
The coal gangue comprises the following components in percentage by weight: SiO22 52～67％，Fe2O3 1.3～6.8％，Al2O3 19～ 35％，MgO 0.5～2.3％，TiO2 0～1.4％，CaO0.4～2.5％，K2O and Na2O1.4～3.9％。
The fly ash comprises the following components in percentage by weight: SiO22 40～60％，Fe2O3 1.0～8.0％，Al2O312％～ 31％，MgO 1.0～4.5％，CaO5.0～18.0％，TiO2 0～1.2％，K2O and Na2O1.1～4.5％。
The weight percentage of silicon dioxide in the quartz sand is more than 98 percent.
The titanium-selecting tailings comprise the following components in percentage by weight: SiO22 39～50％，TiO22.3～10.0％，Fe2O3 1.0～ 5.0％,Al2O38.6％～18.3％，MgO 1.2～5.5％，CaO7.0～18％，BaO0.3～1.8％，B2O3 0.1～0.5％， K2O and Na2O2.5～5.3％。
The method for preparing the continuous basalt fibers by using the blast furnace slag is characterized by comprising the following steps:
(1) pretreatment of raw materials: mixing blast furnace slag, coal gangue, fly ash, quartz sand, zirconia, cerium oxide and titanium tailings, and performing ball milling by using a ball mill, wherein ball milling materials completely pass through a 100-mesh sieve to obtain a mixed material;
(2) uniformly melting raw materials: pouring the mixed material obtained in the step (1) into a smelting furnace for smelting to form uniform melt; wherein the melting temperature is 1400-1600 ℃, and the melting time is 3-5 h;
(3) drawing a bushing: and (3) when the melting time in the step (2) reaches the preset time, reducing the melting temperature to 1300-1450 ℃, and then drawing wires by adopting a platinum-rhodium alloy bushing with 200 holes to obtain the continuous basalt fibers.
The invention has the beneficial effects that: (1) the continuous basalt fiber prepared by the invention takes industrial solid waste blast furnace slag, fly ash and coal gangue as main raw materials, and then quartz sand, zirconia, cerium oxide and titanium tailings are added to reasonably match the content of each component, so as to achieve the purpose of synergistic effect of each component, and effectively realize the high-efficiency utilization of the industrial solid waste. (2) The invention properly improves CaO、TiO2And ZrO2In an amount such that the basalt fiber forms SiO2-Al2O3-CaO-MgO -TiO2-ZrO2System to impart higher elastic modulus and strength to the fiber. CaO belongs to network exosomatic ions, so that the high-temperature viscosity of the melt can be reduced, and the forming speed of the melt is accelerated, so that the fiber has shorter material property and is beneficial to wire drawing forming; TiO22Generally, an octahedral coordination structure exists in a network structure, and is an extranet oxide, so that the melting condition of glass can be improved, and the fluxing function is achieved; ZrO (ZrO)2The strength, thermal stability and corrosion resistance of the glass can be significantly increased.
Detailed Description
The present invention will be further described with reference to the following specific examples, which are intended to be illustrative of the preferred embodiments of the present invention and are not to be construed as limiting the invention in any way.
The blast furnace slag is taken from a certain steel mill in Liudao water city, Guizhou province and comprises the following components in percentage by weight: SiO22 42～48％， Al2O3 7～13％，Fe2O3 0.3～0.7％，CaO33～42％，MgO5～9％，K2O and Na2O1.5～2.5％。
The coal gangue is taken from Liudianshui city of Guizhou province and contains the following components in percentage by weight: SiO22 55～67％，Fe2O3 1.6～ 3.8％，Al2O3 25～33％，MgO 0.8～2.2％，TiO2 0.8～1.2％，CaO0.7～2.1％，K2O and Na2O1.5～3.0％。
The fly ash is taken from a certain power plant in Liudao water city of Guizhou province and comprises the following components in percentage by weight: SiO22 45～55％， Fe2O3 1.2～5.4％，Al2O318％～25％，MgO 1.4～2.6％，CaO5.5～15.6％，TiO2 0～0.8％，K2O and Na2O2.6～3.5％。
The titanium-selecting tailings are obtained from a certain titanium-selecting factory in Qinglong county of Guizhou province, and comprise the following components in percentage by weight: SiO22 44～50％， TiO24.4～7.9％，Fe2O3 1.4～3.7％,Al2O311.4％～18.3％，MgO1.5～4.8％，CaO8～17％，BaO0.7～ 1.5％，B2O3 0.1～0.5％，K2O and Na2O2.5～5.0％。
Example 1: method for preparing continuous basalt fibers from blast furnace slag
1. The composition of the raw materials is shown in Table 2
TABLE 2 raw material composition
| Composition (I) | Weight/kg |
| Blast furnace slag | 33 |
| Coal gangue | 29 |
| Fly ash | 45 |
| Quartz sand | 19 |
| Titanium-selecting tailings | 16 |
| Cerium oxide | 2.4 |
| Zirconium oxide | 2.9 |
2. Preparation of continuous basalt fiber
(1) Pretreatment of raw materials: mixing blast furnace slag, coal gangue, fly ash, quartz sand, zirconia, cerium oxide and titanium tailings, and performing ball milling by using a ball mill, wherein ball milling materials completely pass through a 100-mesh sieve to obtain a mixed material;
(2) uniformly melting raw materials: pouring the mixed material obtained in the step (1) into a smelting furnace for smelting to form uniform melt; wherein the melting temperature is 1450 ℃, and the melting time is 5 h;
(3) drawing a bushing: and (3) when the melting time in the step (2) reaches the preset time, reducing the melting temperature to 1350 ℃, and drawing wires by adopting a platinum-rhodium alloy bushing with 200 holes to obtain the continuous basalt fiber.
Example 2
1. The composition of the raw materials is shown in Table 3
TABLE 3 composition of the raw materials
| Composition (I) | Weight/kg |
| Blast furnace slag | 40 |
| Coal gangue | 35 |
| Fly ash | 42 |
| Quartz sand | 23 |
| Titanium-selecting tailings | 17 |
| Cerium oxide | 2.6 |
| Zirconium oxide | 3.1 |
2. Preparation of continuous basalt fiber
(1) Pretreatment of raw materials: mixing blast furnace slag, coal gangue, fly ash, quartz sand, zirconia, cerium oxide and titanium tailings, and performing ball milling by using a ball mill, wherein ball milling materials completely pass through a 100-mesh sieve to obtain a mixed material;
(2) uniformly melting raw materials: pouring the mixed material obtained in the step (1) into a smelting furnace for smelting to form uniform melt; wherein the melting temperature is 1500 ℃, and the melting time is 4 h;
(3) drawing a bushing: and (3) when the melting time in the step (2) reaches the preset time, reducing the melting temperature to 1400 ℃, and drawing wires by adopting a platinum-rhodium alloy bushing with 200 holes to obtain the continuous basalt fiber.
Example 3
1. The composition of the raw materials is shown in Table 4
TABLE 4 composition of the raw materials
| Composition (I) | Weight/kg |
| Blast furnace slag | 33 |
| Coal gangue | 29 |
| Fly ash | 45 |
| Quartz sand | 19 |
| Titanium-selecting tailings | 16 |
| Cerium oxide | 2.4 |
| Zirconium oxide | 2.9 |
2. Preparation of continuous basalt fiber
(1) Pretreatment of raw materials: mixing blast furnace slag, coal gangue, fly ash, quartz sand, zirconia, cerium oxide and titanium tailings, and performing ball milling by using a ball mill, wherein ball milling materials completely pass through a 100-mesh sieve to obtain a mixed material;
(2) uniformly melting raw materials: pouring the mixed material obtained in the step (1) into a smelting furnace for smelting to form uniform melt; wherein the melting temperature is 1600 ℃, and the melting time is 3 h;
(3) drawing a bushing: and (3) when the melting time in the step (2) reaches the preset time, reducing the melting temperature to 1450 ℃, and then drawing wires by adopting a platinum-rhodium alloy bushing with 200 holes to obtain the continuous basalt fiber.
The above examples 1 to 3 and the prepared continuous basalt fiber were subjected to performance test experiments, and the test experiment results are shown in table 5.
TABLE 5 tensile Strength of the monofilaments
| Numbering | Tensile strength/MPa |
| Example 1 | 2691 |
| Example 2 | 2634 |
| Example 3 | 2623 |
Analysis of the experimental data shows that the continuous basalt fiber monofilaments prepared in the embodiments 1 to 3 have high tensile strength which is higher than 2600 MPa.
Claims (4)
1. The method for preparing the continuous basalt fiber by using the blast furnace slag is characterized in that the continuous basalt fiber consists of the following components in parts by weight: 20-40 parts of blast furnace slag, 25-35 parts of coal gangue, 31-46 parts of fly ash, 10-23 parts of quartz sand, 2.5-4.3 parts of zirconia, 2.1-2.9 parts of cerium oxide and 10-19 parts of titanium tailings;
the method comprises the following steps:
(1) pretreatment of raw materials: mixing blast furnace slag, coal gangue, fly ash, quartz sand, zirconia, cerium oxide and titanium tailings, and performing ball milling by using a ball mill, wherein ball milling materials completely pass through a 100-mesh sieve to obtain a mixed material;
(2) uniformly melting raw materials: pouring the mixed material obtained in the step (1) into a smelting furnace for smelting to form uniform melt; wherein the melting temperature is 1400-1600 ℃, and the melting time is 3-5 h;
(3) drawing a bushing: when the melting time in the step (2) reaches a preset time, reducing the melting temperature to 1300-1450 ℃, and then drawing wires by using a platinum-rhodium alloy bushing with 200 holes to obtain continuous basalt fibers;
the coal gangue comprises the following components in percentage by weight: 252-67% of SiO, 31.3-6.8% of Fe2O31, 319-35% of Al2O, 0.5-2.3% of MgO, 20-1.4% of TiO, 0.4-2.5% of CaO0, K2O and 1.4-3.9% of Na2O1;
the fly ash comprises the following components in percentage by weight: 240-60% of SiO, 31.0-8.0% of Fe2O31, 312-31% of Al2O, 1.0-4.5% of MgO, 5.0-18.0% of CaO5, 20-1.2% of TiO, 3-5% of K2O and 4.1-4.5% of Na2O1.
2. The method for preparing continuous basalt fiber from blast furnace slag according to claim 1, wherein the blast furnace slag comprises the following components in percentage by weight: SiO 235-48%, Al2O 37-18%, Fe2O30.1-0.7%, CaO 29-46%, MgO 4-13%, K2O and Na2O1.1-2.5%.
3. The method for preparing continuous basalt fiber using blast furnace slag according to claim 1, wherein the silica content of the silica sand is more than 98% by weight.
4. The method for preparing the continuous basalt fiber by using the blast furnace slag according to the claim 1, wherein the titanium tailings comprise the following components in percentage by weight: 239-50% of SiO, 22.3-10.0% of TiO22, 31.0-5.0% of Fe2O31.6-18.3% of Al2O38.2-5.5% of MgO, 7.0-18% of CaO7, 0.3-1.8% of BaO0.3, B2O30.1-0.5% of K2O and 5.3% of Na2O2.5.
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| CN111517659B (en) * | 2020-03-05 | 2022-07-08 | 西南科技大学 | Raw material batch for preparing magma rock fiber and preparation method of magma rock fiber |
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