CN1410556A - Aluminium slag ball and its preparation method - Google Patents
Aluminium slag ball and its preparation method Download PDFInfo
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- CN1410556A CN1410556A CN02138450A CN02138450A CN1410556A CN 1410556 A CN1410556 A CN 1410556A CN 02138450 A CN02138450 A CN 02138450A CN 02138450 A CN02138450 A CN 02138450A CN 1410556 A CN1410556 A CN 1410556A
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Abstract
An aluminium slag ball for smelting clean or superclean steel contains aluminium, fluorspar, calcium carbonate, alumina, SiO2, small amount of water, P, S and Cu. Its advantages are simple sphericizing process, high spreadability on the surface of molten steel, excellent insulating performance, and synchronization of deoxidizing and refining.
Description
Technical Field
The invention relates to a molten steel external treatment and refining and alloying technology, in particular to an additive for molten steel surface heat preservation and molten steel refining, which is particularly suitable for smeltingpure or ultra-pure steel from aluminum killed steel, can quickly generate a heat preservation agent covering the surface of molten steel after being added during initial tapping, has strong deoxidation effect and is synthesized into a refining agent with good performance after being transferred to a refining furnace along with molten steel, and can also perform alloying treatment on the molten steel.
Background
As is well known, with the increasing requirements of national economy on steel grades and quality thereof, the steel smelting technology is developed from the original one-step steelmaking into two-step steelmaking, namely, the two-step steelmaking is carried out by primary smelting and refining. The temperature of molten steel and the content of main elements are controlled by primary smelting, and deoxidation, impurity removal and alloying treatment are carried out by refining to obtain the steel grade with expected variety and quality.
In steel making, a heat insulating agent is covered on the surface of molten steel before primary molten steel enters a refining furnace to prevent molten steel from cooling and surface oxidation, then deoxidation and alloying treatment are carried out after the primary molten steel enters the refining furnace, and refining slag with certain components is generated to adsorb deoxidation products and other impurities in steel, so that the aim of purifying the molten steel is fulfilled.
The prior art for the heat preservation measure of the surface of molten steel is roughly divided into three types: firstly, the molten steel is discharged with slag, and the slag cover on the surface of the molten steel is used for insulating and preserving the heat of the molten steel, so that the molten steel is subjected to mass impurity recovery due to the reduction of the steel slag during therefining process. Secondly, the molten steel is discharged without slag, and carbonaceous heat insulating agent (such as carbonized rice husk) with better heat insulating property is added on the surface of the molten steel to insulate and insulate the molten steel, but the recarburization effect of the carbonaceous heat insulating agent on the molten steel is extremely unfavorable for smelting low-carbon steel. Thirdly, a carbon-free protective agent mainly comprising coal dust is adopted, and although the protective agent avoids the recarburization of molten steel, the main component Al in the coal dust2O3And SiO2On the one hand during the refining phaseThe phenomenon of 'silicon return' of molten steel caused by reduction is very unfavorable for smelting certain steel types (such as deep drawing sheet steel) with strictly controlled silicon content, and on the other hand, a large amount of Al2O3Consuming large amount of CaO (lime powder) to form CaAl2O4(calcium metaaluminate) floating as slag, otherwise to reduce Al in steel2O3Inclusion is also disadvantageous.
The deoxidation of molten steel (especially aluminium killed steel) finally uses metal aluminium, and the deoxidation product Al2O3The melting point of the alloy is 2050 ℃, the alloy exists in a dendritic or needle shape in molten steel, and dendritic or needle-shaped oxide inclusions are generated in the steel when the molten steel is condensed, so that the quality of steel is influenced. In the prior art, on the one hand, complex deoxidizers (e.g. ferro-silico-aluminum, ferro-manganese-aluminum) are used to form Al2O3.SiO2Or MnO. Al2O3The eutectic with low melting point facilitates slagging and floating, but the method has limited application range because silicon is difficult to form in the presence of a large amount ofmetallic aluminum orOxides of manganese, not suitable for use in aluminum killed steel; the aluminum-calcium-iron alloy and the aluminum-barium-iron alloy researched in the field of iron alloys replace aluminum-silicon-iron alloy and aluminum-manganese-iron alloy, so that the problem of composite slagging of the deoxidation product of the aluminum killed steel is solved, but no successful report is found at present. Another aspect is the addition of calcium oxide to the molten steel during refining to form cao2O3The (calcium metaaluminate) eutectic with low melting point is slagged and floated, but the method is that before deoxidation, the composite slagged of deoxidation products is followed, and Al dispersed in steel2O3Takes a long time to combine with CaO into slag to float upwards and remove Al2O3The kinetic conditions of (a) are far from ideal.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the aluminum slag ball with low content of harmful impurities and the preparation method thereof, which are suitable for smelting pure or ultra-pure steel by using aluminum killed steel and can quickly generate a heat insulating agent covering the surface of molten steel after initial smelting and tapping.
The technical scheme adopted by the invention for solving the technical problems is as follows: an aluminum slag ball contains aluminum (Al) and fluorite (CaF)2) Calcium carbonate (CaCO)3) Aluminum oxide (Al)2O3) Silicon dioxide (SiO)2) And a small amount of water (H)2O), phosphorus (P), sulfur (S), copper (Cu) and other inevitable impurities, and the content of the components is (weight percent): 10-45 parts of aluminum; 5-35% of aluminum oxide; 10-60 parts of fluorite; 5-15 parts of calcium carbonate;silicon dioxide is less than or equal to 5; the water content is less than or equal to 0.5; phosphorus is less than or equal to 0.02; sulfur is less than or equal to 0.15; copper is less than or equal to 0.3; the balance of other materials.
In order to meet the requirements of different steel grades, the steel further comprises the following components in percentage by weight: 20-30 parts of aluminum; 10-15 parts of aluminum oxide; 40-50 parts of fluorite; 10-12 parts of calcium carbonate; silicon dioxide is less than or equal to 5; the water content is less than or equal to 0.5; phosphorus is less than or equal to 0.02; sulfur is less than or equal to 0.15; copper is less than or equal to 0.3; the balance of other materials.
Furthermore, the composition content is (weight percent): 10-20 parts of aluminum; 20-30 parts of aluminum oxide; 40-50 parts of fluorite; 10-15 parts of calcium carbonate; silicon dioxide is less than or equal to 5; the water content is less than or equal to 0.5; phosphorus is less than or equal to 0.02; sulfur is less than or equal to 0.15; copper is less than or equal to 0.3; the balance of other materials.
Furthermore, the composition content is (weight percent): 23.5-26.5% of aluminum; 10-15 parts of aluminum oxide; 43.5-46.5% fluorite; 10-12 parts of calcium carbonate; silicon dioxide is less than or equal to 5; the water content is less than or equal to 0.5; phosphorus is less than or equal to 0.02; sulfur is less than or equal to 0.15; copper is less than or equal to 0.3; the balance of other materials.
Furthermore, the composition content is (weight percent): 20-25 parts of aluminum; 30-35% of aluminum oxide; 20-35 parts of fluorite; 10-15 parts of calcium carbonate; silicon dioxide is less than or equal to 5; the water content is less than or equal to 0.5; phosphorus is less than or equal to 0.02; sulfur is less than or equal to 0.15; copper is less than or equal to 0.3; the balance of other materials.
A preparation method of aluminum slag balls comprises the following process flows: purchasing and storing the metal aluminum particles, the aluminum slag powder, the fluorite concentrate, the high-quality limestone powder and the glass water which are sampled and analyzed to be qualified in place, weighing and proportioning the raw materials which are tested to be qualified, putting the raw materials into a mixer to be uniformly mixed, adding the glass water to be uniformly mixed, putting the materials into a double-roller ball press to be rolled into balls, and drying the balls by a drying device to obtain the finished product.
Further, the chemical components of the raw materials are respectively as follows (weight percent):
aluminum particles: al is more than or equal to 95 percent, Cu is less than or equal to 0.5 percent, and Si is less than or equal to 3 percent;
aluminum slag powder: al is more than or equal to 40 percent, and Al2O3≤55％，SiO2≤5％；
Fluorite powder: CaF2≥98％，SiO2≤1％，S≤0.05％，P≤0.03％；
Limestone powder: CaCO3≥95％，SiO2≤2％，S≤0.05％，P≤0.01％。
When the aluminum slag ball is added into a ladle after tapping, the ball-shaped material has good fluidity, so that the aluminum slag ball is easy to be castA covering layer can be quickly formed on the surface of the molten steel; under the heating action of molten steel, calcium carbonate in the material is decomposed at about 1000 ℃ to generate CO2The gas makes the sphere burst and disperse to form loose powder which plays a role in preserving the heat of the surface ofthe molten steel. Escaping CO2The gas is discharged from the surface of the molten steel to preventStopping oxidation of the molten steel, CaCO due to the heat-insulating effect of the powdery material3The temperature rise decomposition is not violent and is continued for a period of time so as to meet the time requirement from tapping to refining. In the refining period, the powder is melted under the stirring condition and participates in the deoxidation reaction of the molten steel,
the deoxidation product alumina reacts with calcium fluoride in the fluorite powder,
the generated aluminum trifluoride is escaped as gas, the generated calcium oxide is continuously combined with the deoxidation product aluminum oxide,
the reaction and the combination process are carried out simultaneously, the dynamic condition of the deoxidized product physical and chemical synthetic slag is very favorable, and CaAl is finally generated2O4The slag phase mainly comprises (calcium metaaluminate), the theoretical melting point of the slag is 1575 ℃, when more than 10 percent of calcium fluoride and a small amount of silicon dioxide exist, the melting point can be reduced to about 1400 ℃, the slag phase has larger interphase tension with molten steel, can well float up to form slag without forming inclusion in the steel, and is more beneficial to the purity of the molten steel.
When partial aluminum slag powder is used for replacing metal aluminum powder and partial calcium carbonate powder is used for replacing fluorite powder, the main components of the aluminum slag ball are metal aluminum, calcium fluoride, calcium carbonate, aluminum oxide and silicon dioxide, and the deoxidation and refining reaction can be expressed by the following formula:
the oxygen in the reactant on the left side of the upper formula is from molten steel, and the rest substances are heat preservation and refining agent components, and each kilogram of the heat preservation and refining agent componentsThe above materials can combine about 0.25 kg of oxygen and CO2Gas evolution during incubation, AlF3The gas is removed during the deoxygenation refining.
The aluminium shot as described above, to which the alloying agent can be added, most typically the components are Al, Ti, Al can be added in the form of aluminium shot, the other components can be added in the form of powders of iron alloy, the amount added can vary within a considerable range, up to 20% by weight, to suit the steel alloying needs. Because a large amount of metallic aluminum is used as protection in the base material, the added alloying elements have little oxidation loss and stable yield.
The above aluminum slag balls can be added with carbonates of Ba, Mg, K, Na and Li to partially or completely replace calcium carbonate, and when the total amount of the carbonates is below 15%, the use is not affected. The oxide pair of these alkali metals or alkaline earth metals is CaAl2O4The slag phase mainly containing calcium metaaluminate can play a role in modifying, deteriorating and changing the surface tension, thereby being more beneficial to the purity of molten steel.
As for the aluminum slag ball, Ti can be used for partially or completely replacing Al so as to meet the requirements of steel grades (such as stainless steel and the like) deoxidized and alloyed by Ti.
The aluminum slag ball can be added with oxides of vanadium and niobium, and the process of adding alloy components into steel is completed by utilizing the reduction action of aluminum, so that the alloying cost is reduced.
The invention has the advantages that the contents of impurities such as carbon, silicon, sulfur, phosphorus and the like are very low, and the invention is particularly suitable for low-carbon low-silicon pure steel and other ultra-pure steel; the defective heat insulating agents such as fly ash, carbonized rice husk and the like are replaced; the water content is controlled, so that the popping phenomenon that the materials enter molten steel is avoided. And secondly, the component contents of the deoxidizing and alloying elements can be changed in a considerable range, so that the requirements of various steel grades are met. And thirdly, the alkali metal or alkaline earth metal oxide (added in the form of calcium carbonate compound) can be selected at will within a certain content range to meet special requirements on modification, modification and the like of the refined synthetic slag. Fourthly, the raw materials are common and easy to obtain, the balling process is simple and reliable, the composition segregation fluctuation does not exist, the adding process is simple, and the spreading and heat preservation performance of the surface of the molten steel is excellent. And fifthly, deoxidation and refining are carried out synchronously, and oxide inclusions in the molten steel are greatly reduced.
Detailed Description
Preparing aluminum slag balls:
the raw materials respectively comprise the following chemical components in percentage by weight:
aluminum particles: al is more than or equal to 95 percent, Cu is less than or equal to 0.5 percent, and Si is less than or equal to 3 percent;
aluminum slag powder: al is more than or equal to 40 percent, and Al2O3≤55％，SiO2≤5％；
Fluorite powder: CaF2≥98％，SiO2≤1％，S≤0.05％，P≤0.03％；
Limestone powder: CaCO3≥95％，SiO2≤2％，S≤0.05％，P≤0.01％。)
The method is characterized in that metal aluminum particles, aluminum slag powder, fluorite concentrate, high-quality limestone powder and glass water are purchased in place and stored in bins respectively, raw materials are sampled and analyzed, and the raw materials comprise the following chemical components:
aluminum particles: 95.8% of Al, 0.32% of Cu and 2.37% of Si;
aluminum slag powder: 40.29% of Al, Al2O351.36％、SiO23.48％；
Fluorite powder: CaF298.26％、SiO20.67％、S 0.03％、P 0.023％；
Limestone powder: CaCO396.3％、SiO20.52％、S 0.032％、P 0.015％。
Weighing qualified raw materials for assay: 160Kg of aluminum particles, 250Kg of aluminum slag powder, 450Kg of fluorite powder and 125Kg of limestone powder, the weighed raw materials are put into a drum mixer to be uniformly mixed (for 15 minutes), 50Kg of glass water with modulus of 3.5-3.7 is put into the uniformly mixed materials and is uniformly mixed in a stirrer. Rolling the uniformly mixed materials into spherical particles of 10-20 mm in a double-roller ball press, putting the spherical particles into a drying device with a collection bin using coke as fuel, drying at the temperature of about 200 ℃ for 20-24 hours, and screening and warehousing again after the moisture of the finished product is less than 0.5%.
The chemical components of the finished product in the above examples are (weight%):
Al：24.9；
Al2O3：12.5；
CaF2：44.12；
CaCO3：11.78；
SiO2：3.26；
H2O：0.16；
P：0.008；
S：0.079；
Cu：0.144。
test application example: the aluminum slag balls prepared by the method are applied in batches in Shanghai Bao Steel company, and the results show that: the invention has good application manufacturability, can achieve 'complete material and whole process treatment', is simple and convenient to operate, and particularly has the functions of cracking and slagging on the surface of molten steel, good spreading and covering, and strict heat preservation and air isolation. In the refining furnace, stirring is added, so that ideal slag washing capacity is shown, and the slag removing effect is obvious. When alloying treatment is needed, the invention which is prepared by adding alloying elements containing needed alloying elements is used for alloying treatment, the yield of the alloying elements is greatly improved, the effect is very obvious, and the invention is appreciated by stokehold technicians and operators.
Claims (7)
1. An aluminum slag ball contains aluminum (Al) and fluorite (CaF)2) Calcium carbonate (CaCO)3) Aluminumoxide (Al)2O3) Silicon dioxide (SiO)2) And a small amount of water (H)2O), phosphorus (P), sulfur (S), copper (Cu) and other inevitable impurities, characterized in that it comprises, in weight percent: 10-45 parts of aluminum; 5-35% of aluminum oxide; 10-60 parts of fluorite; 5-15 parts of calcium carbonate; silicon dioxide is less than or equal to 5; the water content is less than or equal to 0.5; phosphorus is less than or equal to 0.02; sulfur is less than or equal to 0.15; copper is less than or equal to 0.3; the balance of other materials.
2. The aluminum dross pellet of claim 1, wherein the composition comprises, in weight%: 20-30 parts of aluminum; 10-15 parts of aluminum oxide; 40-50 parts of fluorite; 10-12 parts of calcium carbonate; silicon dioxide is less than or equal to 5; the water content is less than or equal to 0.5; phosphorus is less than or equal to 0.02; sulfur is less than or equal to 0.15; copper is less than or equal to 0.3; the balance of other materials.
3. The aluminum dross pellet of claim 1, wherein the composition comprises, in weight%: 10-20 parts of aluminum; 20-30 parts of aluminum oxide; 40-50 parts of fluorite; 10-15 parts of calcium carbonate; silicon dioxide is less than or equal to 5; the water content is less than or equal to 0.5; phosphorus is less than or equal to 0.02; sulfur is less than or equal to 0.15; copper is less than or equal to 0.3; the balance of other materials.
4. The aluminum dross pellet of claim 1, wherein the composition comprises, in weight%: 23.5-26.5% of aluminum; 10-15 parts of aluminum oxide; 43.5-46.5% fluorite; 10-12 parts of calcium carbonate; silicon dioxide is less than or equal to 5; the water content is less than or equal to 0.5; phosphorus is less than or equal to 0.02; sulfur is less than or equal to 0.15; copper is less than or equal to 0.3; the balance of other materials.
5. The aluminum dross pellet of claim 1, wherein the composition comprises, in weight%: 20-25 parts of aluminum; 30-35% of aluminum oxide; 20-35 parts of fluorite; 10-15 parts of calcium carbonate; silicon dioxide is less than or equal to 5; the water content is less than or equal to 0.5; phosphorus is less than or equal to 0.02; sulfur is less than or equal to 0.15; copper is less than or equal to 0.3; the balance of other materials.
6. The preparation method of the aluminum slag ball is characterized by comprising the following process flows: purchasing and storing the metal aluminum particles, the aluminum slag powder, the fluorite concentrate, the high-quality limestone powder and the glass water which are sampled and analyzed to be qualified in place, weighing and proportioning the raw materials which are tested to be qualified, putting the raw materials into a mixer to be uniformly mixed, adding the glass water to be uniformly mixed, putting the materials into a double-roller ball press to be rolled into balls, and drying the balls by a drying device to obtain the finished product.
7. The method for preparing aluminum dross pellets of claim 6, wherein: the chemical components of the raw materials are as follows (weight percent):
aluminum particles: al is more than or equal to 95 percent, Cu is less than or equal to 0.5 percent, and Si is less than or equal to 3 percent;
aluminum slag powder: al is more than or equal to 40 percent, and Al2O3≤55％，SiO2≤5％；
Fluorite powder: CaF2≥98％，SiO2≤1％，S≤0.05％，P≤0.03％；
Limestone powder: CaCO3≥95％，SiO2≤2％，S≤0.05％，P≤0.01％。
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324150C (en) * | 2005-03-30 | 2007-07-04 | 上海宝越耐火材料有限公司 | Slag from aluminum smelting for making clean steel and method for preparing same |
| CN100422349C (en) * | 2005-10-11 | 2008-10-01 | 梅一峰 | Prefused refined slag modified aluminium slag ball and its preparing method |
| CN102071286A (en) * | 2011-01-26 | 2011-05-25 | 天津钢铁集团有限公司 | Compound aluminum reducing agent for steelmaking and refining |
| CN101676410B (en) * | 2008-09-18 | 2011-06-29 | 宝山钢铁股份有限公司 | Aluminum slag, desulfurizer and desulfurizing method for desulfurization of high silicon molten iron |
| CN102851452A (en) * | 2012-10-08 | 2013-01-02 | 太原钢铁(集团)有限公司 | Slag pressing agent and preparation method thereof |
| CN104946850A (en) * | 2015-06-13 | 2015-09-30 | 秦皇岛首秦金属材料有限公司 | Converter tapping slag washing method using low-Al alumina ball |
| CN105349734A (en) * | 2015-12-08 | 2016-02-24 | 钢城集团凉山瑞海实业有限公司 | Method adopting steel ladle casting residues and tailings for preparing high-aluminum slag modifier pellets and application thereof |
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2002
- 2002-10-17 CN CNB021384509A patent/CN1186465C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324150C (en) * | 2005-03-30 | 2007-07-04 | 上海宝越耐火材料有限公司 | Slag from aluminum smelting for making clean steel and method for preparing same |
| CN100422349C (en) * | 2005-10-11 | 2008-10-01 | 梅一峰 | Prefused refined slag modified aluminium slag ball and its preparing method |
| CN101676410B (en) * | 2008-09-18 | 2011-06-29 | 宝山钢铁股份有限公司 | Aluminum slag, desulfurizer and desulfurizing method for desulfurization of high silicon molten iron |
| CN102071286A (en) * | 2011-01-26 | 2011-05-25 | 天津钢铁集团有限公司 | Compound aluminum reducing agent for steelmaking and refining |
| CN102851452A (en) * | 2012-10-08 | 2013-01-02 | 太原钢铁(集团)有限公司 | Slag pressing agent and preparation method thereof |
| CN102851452B (en) * | 2012-10-08 | 2014-05-07 | 太原钢铁(集团)有限公司 | Slag pressing agent and preparation method thereof |
| CN104946850A (en) * | 2015-06-13 | 2015-09-30 | 秦皇岛首秦金属材料有限公司 | Converter tapping slag washing method using low-Al alumina ball |
| CN104946850B (en) * | 2015-06-13 | 2017-12-15 | 秦皇岛首秦金属材料有限公司 | A kind of converter tapping uses low Al alumina balls wash heat method |
| CN105349734A (en) * | 2015-12-08 | 2016-02-24 | 钢城集团凉山瑞海实业有限公司 | Method adopting steel ladle casting residues and tailings for preparing high-aluminum slag modifier pellets and application thereof |
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Assignee: Changzhou ChangWu charging Co., Ltd Assignor: Jiangnan Iron Alloy Co., Ltd, Jiangsu Contract fulfillment period: 2007.3.12 to 2015.3.11 Contract record no.: 2008320000666 Denomination of invention: High alumina slag ball and preparing method thereof Granted publication date: 20050126 License type: Exclusive license Record date: 2008.10.9 |
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