CN109626833A - A method of continuous basalt fiber is prepared with blast furnace slag - Google Patents

A method of continuous basalt fiber is prepared with blast furnace slag Download PDF

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Publication number
CN109626833A
CN109626833A CN201811115337.1A CN201811115337A CN109626833A CN 109626833 A CN109626833 A CN 109626833A CN 201811115337 A CN201811115337 A CN 201811115337A CN 109626833 A CN109626833 A CN 109626833A
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Prior art keywords
blast furnace
furnace slag
basalt fiber
continuous basalt
parts
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CN109626833B (en
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高昭宗
蔡菲
张大忠
喻荣玲
邢双梅
齐晶
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Shougang Shuicheng Iron And Steel (group) Saide Construction Co Ltd
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Shougang Shuicheng Iron And Steel (group) Saide Construction Co Ltd
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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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses a kind of methods for preparing continuous basalt fiber with blast furnace slag, it is using industrial solid castoff blast furnace slag, flyash, gangue as primary raw material, quartz sand, zirconium oxide, cerium oxide and Tailing of titanium separation are added again, rational proportion is carried out to each component content, then pass through ball mill ball milling, it mixes each ingredient uniformly, then mixed material is subjected to frit reaction at an appropriate high temperature, most carry out wire drawing through platinum-rhodium alloy bushing afterwards and obtain continuous basalt fiber.The present invention is by properly increasing CaO, TiO2And ZrO2Content, make basalt fibre formed SiO2‑Al2O3‑CaO‑MgO‑TiO2‑ZrO2System reduces the high temperature viscosity of melt, significantly increases intensity, thermal stability and the corrosion resistance of glass；Realize the purpose to industrial solid castoff comprehensive utilization.

Description

A method of continuous basalt fiber is prepared with blast furnace slag
Technical field
The present invention relates to inorfil preparation fields, and in particular to a kind of side that continuous basalt fiber is prepared with blast furnace slag Method.
Background technique
Continuous basalt fiber (Continuous Basalt Fibre abbreviation CBF or BF) is that a kind of environmental protection inorganic is fine Material is tieed up, there are the excellent properties such as high-strength light, high temperature resistant, corrosion-resistant, anti-oxidant, radiation protection, thermal acoustic insulation, is navigated in space flight The fields such as sky, automobile ship, civil engineering traffic, energy environment, chemical industry fire-fighting, defence and military have widely used.Especially building It builds in field, as the novel enhanced material of cement, part substitutes reinforcing bar, and with cement, concrete with compatible well Property, it can effectively enhance the intensity and cracking resistance of cement-based material.
Currently, the raw material for preparing basalt fibre mainly exploits natural basalt, and for preparing basalt fibre Raw material research it is less.For preparing the natural basalt of basalt fibre, main component is as shown in table 1.
Table 1 is used to prepare the natural basalt component of basalt fibre
Ingredient SiO2 Al2O3 Fe2O3+FeO CaO MgO+MnO TiO2 Other
Content/% 45~55 12~18 4.5~14 5~12 3.0~7.0 0.9~2.0 2.0~3.5
Blast furnace slag be in ironmaking by ash content and flux in gangue in ore, fuel non-volatilization component and some other A kind of mixture of the impurity composition in the pig iron is not can enter.In general, when furnace charge grade is up to 60~66%, 1 ton is often produced The pig iron can produce 250~350kg of clinker.With China produce per year 8 tons of the pig iron calculating, annual blast furnace slag yield up to 2.4 hundred million tons with On, the nearly one third of proportion in all industrial residue discharge amount shares.And the blast furnace slag overall utilization in China compared with It is low, blast furnace slag total amount 50% is not reached, a large amount of blast furnace slag is accumulated exerts heavy pressures on to ecological environment.Blast furnace slag it is main at Part has SiO2、CaO、 Al2O3、Fe2O3, MnO, MgO etc., it is similar to basaltic ingredient, therefore, can by adding related raw material, To reach the content of main component corresponding with basalt, to realize the resource reutilization of blast furnace slag.
Summary of the invention
The purpose of the present invention is to provide a kind of method for preparing continuous basalt fiber as primary raw material using blast furnace slag, with Realize the resource reutilization of trade waste blast furnace slag.
To achieve the above object, The technical solution adopted by the invention is as follows:
A method of continuous basalt fiber is prepared with blast furnace slag, which is characterized in that the continuous basalt fiber is by weight Percentage is measured, includes its following component: 20~40 parts of blast furnace slag, 25~35 parts of gangue, 31~46 parts of flyash, quartz sand 10~23 parts, 2.5~4.3 parts of zirconium oxide, 2.1~2.9 parts of cerium oxide, 10~19 parts of Tailing of titanium separation.
The blast furnace slag contains the ingredient of following weight percent: SiO235~48%, Al2O37~18%, Fe2O3 0.1~0.7%, CaO29~46%, MgO 4~13%, K2O and Na2O1.1~2.5%.
The gangue contains the ingredient of following weight percent: SiO252~67%, Fe2O31.3~6.8%, Al2O319~35%, MgO 0.5~2.3%, TiO20~1.4%, CaO0.4~2.5%, K2O and Na2O1.4~3.9%.
The flyash contains the ingredient of following weight percent: SiO240~60%, Fe2O31.0~8.0%, Al2O312%~31%, MgO 1.0~4.5%, CaO5.0~18.0%, TiO20~1.2%, K2O and Na2O1.1~ 4.5%.
Silica weight percentage is greater than 98% in the quartz sand.
The Tailing of titanium separation contains the ingredient of following weight percent: SiO239~50%, TiO22.3~10.0%, Fe2O31.0~5.0%, Al2O38.6%~18.3%, MgO 1.2~5.5%, CaO7.0~18%, BaO0.3~ 1.8%, B2O30.1~0.5%, K2O and Na2O2.5~5.3%.
A kind of method preparing continuous basalt fiber with blast furnace slag, which is characterized in that the method includes with Lower step:
(1) pretreatment of raw material: by blast furnace slag, gangue, flyash, quartz sand, zirconium oxide, cerium oxide and Tailing of titanium separation into Row mixes and carries out ball milling with ball mill, and ball milling material is made to pass through 100 mesh sieve completely, obtains mixed material；
(2) raw material molten homogeneous: the mixed material that step (1) obtains is poured into smelting furnace and is melted, mixed material is made Form uniform melt；Wherein, fusion temperature is 1400~1600 DEG C, and fusing time is 3~5h；
(3) bushing wire drawing: after the fusing time of step (2) reaches the predetermined time, fusion temperature is down to 1300~ 1450 DEG C, then wire drawing is carried out using 200 hole platinum-rhodium alloy bushings to get continuous basalt fiber.
Beneficial effects of the present invention: (1) continuous basalt fiber prepared by the present invention is with industrial solid castoff blast furnace Slag, flyash, gangue are primary raw material, then add quartz sand, zirconium oxide, cerium oxide and Tailing of titanium separation, to each component content Rational proportion is carried out, to achieve the purpose that each ingredient synergistic effect, effectively realizes the efficient benefit to industrial solid castoff With.(2) present invention is by properly increasing CaO, TiO2And ZrO2Content, make basalt fibre formed SiO2-Al2O3-CaO- MgO -TiO2-ZrO2System, to assign the higher elasticity modulus of fiber and intensity.Wherein, CaO belongs to network-modifying ion, can The high temperature viscosity of melt is reduced, while accelerating the shaping speed of melt, makes fiber that there is shorter material, is conducive to wire-drawing shape； TiO2Generally it is present in network structure with octahedral coordination structure, is network modifying oxide, being melted for glass can be improved Condition plays fluxing action；ZrO2Intensity, thermal stability and the corrosion resistance of glass can be dramatically increased.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described, and following embodiments are only preferable realities of the invention Example is applied, is not intended to limit the present invention in any form.
Blast furnace slag is derived from Guizhou Province's Lupanshui City steel mill, the ingredient containing following weight percent: SiO242~ 48%, Al2O37~13%, Fe2O30.3~0.7%, CaO33~42%, MgO5~9%, K2O and Na2O1.5~2.5%.
Gangue is derived from Guizhou Province's Lupanshui City, the ingredient containing following weight percent: SiO255~67%, Fe2O31.6~3.8%, Al2O325~33%, MgO 0.8~2.2%, TiO20.8~1.2%, CaO0.7~2.1%, K2O and Na2O1.5~3.0%.
Flyash is derived from Guizhou Province Lupanshui City power plant, the ingredient containing following weight percent: SiO245~ 55%, Fe2O31.2~5.4%, Al2O318%~25%, MgO 1.4~2.6%, CaO5.5~15.6%, TiO20~ 0.8%, K2O and Na2O2.6~3.5%.
Tailing of titanium separation is derived from Guizhou Province Qinglong County Xuan Tai factory, the ingredient containing following weight percent: SiO244~ 50%, TiO24.4~7.9%, Fe2O31.4~3.7%, Al2O311.4%~18.3%, MgO1.5~4.8%, CaO8~ 17%, BaO0.7~1.5%, B2O30.1~0.5%, K2O and Na2O2.5~5.0%.
Embodiment 1: a method of continuous basalt fiber is prepared with blast furnace slag
1, raw material composition is shown in Table 2
2 raw material of table composition
Ingredient Weight/kg
Blast furnace slag 33
Gangue 29
Flyash 45
Quartz sand 19
Tailing of titanium separation 16
Cerium oxide 2.4
Zirconium oxide 2.9
2, the preparation of continuous basalt fiber
(1) pretreatment of raw material: by blast furnace slag, gangue, flyash, quartz sand, zirconium oxide, cerium oxide and Tailing of titanium separation into Row mixes and carries out ball milling with ball mill, and ball milling material is made to pass through 100 mesh sieve completely, obtains mixed material；
(2) raw material molten homogeneous: the mixed material that step (1) obtains is poured into smelting furnace and is melted, mixed material is made Form uniform melt；Wherein, fusion temperature is 1450 DEG C, fusing time 5h；
(3) bushing wire drawing: after the fusing time of step (2) reaches the predetermined time, being down to 1350 DEG C for fusion temperature, then Wire drawing is carried out using 200 hole platinum-rhodium alloy bushings to get continuous basalt fiber.
Embodiment 2
1, raw material composition is shown in Table 3
3 raw material of table composition
Ingredient Weight/kg
Blast furnace slag 40
Gangue 35
Flyash 42
Quartz sand 23
Tailing of titanium separation 17
Cerium oxide 2.6
Zirconium oxide 3.1
2, the preparation of continuous basalt fiber
(1) pretreatment of raw material: by blast furnace slag, gangue, flyash, quartz sand, zirconium oxide, cerium oxide and Tailing of titanium separation into Row mixes and carries out ball milling with ball mill, and ball milling material is made to pass through 100 mesh sieve completely, obtains mixed material；
(2) raw material molten homogeneous: the mixed material that step (1) obtains is poured into smelting furnace and is melted, mixed material is made Form uniform melt；Wherein, fusion temperature is 1500 DEG C, fusing time 4h；
(3) bushing wire drawing: after the fusing time of step (2) reaches the predetermined time, being down to 1400 DEG C for fusion temperature, then Wire drawing is carried out using 200 hole platinum-rhodium alloy bushings to get continuous basalt fiber.
Embodiment 3
1, raw material composition is shown in Table 4
4 raw material of table composition
Ingredient Weight/kg
Blast furnace slag 33
Gangue 29
Flyash 45
Quartz sand 19
Tailing of titanium separation 16
Cerium oxide 2.4
Zirconium oxide 2.9
2, the preparation of continuous basalt fiber
(1) pretreatment of raw material: by blast furnace slag, gangue, flyash, quartz sand, zirconium oxide, cerium oxide and Tailing of titanium separation into Row mixes and carries out ball milling with ball mill, and ball milling material is made to pass through 100 mesh sieve completely, obtains mixed material；
(2) raw material molten homogeneous: the mixed material that step (1) obtains is poured into smelting furnace and is melted, mixed material is made Form uniform melt；Wherein, fusion temperature is 1600 DEG C, fusing time 3h；
(3) bushing wire drawing: after the fusing time of step (2) reaches the predetermined time, being down to 1450 DEG C for fusion temperature, then Wire drawing is carried out using 200 hole platinum-rhodium alloy bushings to get continuous basalt fiber.
Above-described embodiment 1-3 and preparation-obtained continuous basalt fiber are tested for the property experiment, test experiments The results are shown in Table 5.
5 monofilament tensile strength of table
Number Tensile strength/Mpa
Embodiment 1 2691
Embodiment 2 2634
Embodiment 3 2623
To above-mentioned analysis of experimental data it is found that the continuous basalt fiber monofilament tensile strength that Examples 1 to 3 is prepared It is higher, reach 2600MPa or more.

Claims (7)

1. a kind of method for preparing continuous basalt fiber with blast furnace slag, which is characterized in that the continuous basalt fiber is by weight Percentage includes its following component: 20~40 parts of blast furnace slag, 25~35 parts of gangue, and 31~46 parts of flyash, quartz sand 10~ 23 parts, 2.5~4.3 parts of zirconium oxide, 2.1~2.9 parts of cerium oxide, 10~19 parts of Tailing of titanium separation.
2. a kind of method for preparing continuous basalt fiber with blast furnace slag according to claim 1, which is characterized in that described Blast furnace slag contain the ingredient of following weight percent: SiO235~48%, Al2O37~18%, Fe2O30.1~0.7%, CaO29~46%, MgO 4~13%, K2O and Na2O1.1~2.5%.
3. a kind of method for preparing continuous basalt fiber with blast furnace slag according to claim 1, which is characterized in that described Gangue contain the ingredient of following weight percent: SiO252~67%, Fe2O31.3~6.8%, Al2O319~35%, MgO 0.5~2.3%, TiO20~1.4%, CaO0.4~2.5%, K2O and Na2O1.4~3.9%.
4. a kind of method for preparing continuous basalt fiber with blast furnace slag according to claim 1, which is characterized in that described Flyash contain the ingredient of following weight percent: SiO240~60%, Fe2O31.0~8.0%, Al2O312%~ 31%, MgO 1.0~4.5%, CaO5.0~18.0%, TiO20~1.2%, K2O and Na2O1.1~4.5%.
5. a kind of method for preparing continuous basalt fiber with blast furnace slag according to claim 1, which is characterized in that described Quartz sand in silica weight percentage be greater than 98%.
6. a kind of method for preparing continuous basalt fiber with blast furnace slag according to claim 1, which is characterized in that described Tailing of titanium separation contain the ingredient of following weight percent: SiO239~50%, TiO22.3~10.0%, Fe2O31.0~ 5.0%, Al2O38.6%~18.3%, MgO 1.2~5.5%, CaO7.0~18%, BaO0.3~1.8%, B2O30.1~ 0.5%, K2O and Na2O2.5~5.3%.
7. a kind of method for preparing continuous basalt fiber with blast furnace slag according to claim 1-6, feature It is, the described method comprises the following steps:
(1) pretreatment of raw material: blast furnace slag, gangue, flyash, quartz sand, zirconium oxide, cerium oxide and Tailing of titanium separation are mixed Merging carries out ball milling with ball mill, and ball milling material is made to pass through 100 mesh sieve completely, obtains mixed material；
(2) raw material molten homogeneous: the mixed material that step (1) obtains is poured into smelting furnace and is melted, mixed material is formed Uniform melt；Wherein, fusion temperature is 1400~1600 DEG C, and fusing time is 3~5h；
(3) bushing wire drawing: after the fusing time of step (2) reaches the predetermined time, being down to 1300~1450 DEG C for fusion temperature, Wire drawing is carried out to get continuous basalt fiber using 200 hole platinum-rhodium alloy bushings again.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111517659A (en) * 2020-03-05 2020-08-11 西南科技大学 Raw material batch for preparing magma rock fiber and preparation method of magma rock fiber
CN113727950A (en) * 2019-04-25 2021-11-30 新日本繊维株式会社 Radiation-resistant inorganic material and fiber thereof

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CN101289274A (en) * 2008-06-06 2008-10-22 北京大学 Process for preparing inorfil by using iron blast-furnace slag and fly ash
CN102276142A (en) * 2011-06-30 2011-12-14 北京大学 Equipment and method for preparing inorganic ore slag fiber by utilizing thermal-state blast furnace slag
CN103539347A (en) * 2012-07-09 2014-01-29 上海华明高技术（集团）有限公司 Inorganic fiber with solid waste as raw material and production method thereof
CN103964697A (en) * 2014-04-23 2014-08-06 东南大学 Basalt fiber composition with high alkali resistance and application method of basalt fiber composition
CN104261669A (en) * 2014-09-25 2015-01-07 北京大学 Method for preparing continuous basalt fiber with industry waste solid as raw material
CN104445909A (en) * 2014-10-31 2015-03-25 湖州吴兴道场城乡建设发展有限公司 Novel slag wool fiberboard
CN105800943A (en) * 2016-03-16 2016-07-27 济南大学 Glass fiber composition with red mud and blast furnace slag as raw materials, alkali-resistant glass fiber and preparation method for alkali-resistant glass fiber

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101289274A (en) * 2008-06-06 2008-10-22 北京大学 Process for preparing inorfil by using iron blast-furnace slag and fly ash
CN102276142A (en) * 2011-06-30 2011-12-14 北京大学 Equipment and method for preparing inorganic ore slag fiber by utilizing thermal-state blast furnace slag
CN103539347A (en) * 2012-07-09 2014-01-29 上海华明高技术（集团）有限公司 Inorganic fiber with solid waste as raw material and production method thereof
CN103964697A (en) * 2014-04-23 2014-08-06 东南大学 Basalt fiber composition with high alkali resistance and application method of basalt fiber composition
CN104261669A (en) * 2014-09-25 2015-01-07 北京大学 Method for preparing continuous basalt fiber with industry waste solid as raw material
CN104445909A (en) * 2014-10-31 2015-03-25 湖州吴兴道场城乡建设发展有限公司 Novel slag wool fiberboard
CN105800943A (en) * 2016-03-16 2016-07-27 济南大学 Glass fiber composition with red mud and blast furnace slag as raw materials, alkali-resistant glass fiber and preparation method for alkali-resistant glass fiber

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113727950A (en) * 2019-04-25 2021-11-30 新日本繊维株式会社 Radiation-resistant inorganic material and fiber thereof
TWI844671B (en) * 2019-04-25 2024-06-11 日商新日本纖維股份有限公司 Radiation-resistant inorganic materials and their fibers
CN111517659A (en) * 2020-03-05 2020-08-11 西南科技大学 Raw material batch for preparing magma rock fiber and preparation method of magma rock fiber
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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