CN101029345A - Production of low-phosphor electroslag melt steel - Google Patents
Production of low-phosphor electroslag melt steel Download PDFInfo
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- CN101029345A CN101029345A CNA200610024228XA CN200610024228A CN101029345A CN 101029345 A CN101029345 A CN 101029345A CN A200610024228X A CNA200610024228X A CN A200610024228XA CN 200610024228 A CN200610024228 A CN 200610024228A CN 101029345 A CN101029345 A CN 101029345A
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Abstract
Production of low-phosphorus electro-slag re-melting steel is carried out by preparing for metal electrode, false electrode, slag containing fluorite, activated lime and arc-striking agent in proportion of CaF2:TiO2=1:1-2 or carbon electrode, striking while slagging by metal electrode, raising current for 5-15mins, re-melting, proportioning with CaO:CaF2=15-25%:75-85%, smelting, controlling current and voltage and slow-cooling. It has less harmful element contents and ferro-silico content, better steel-liquid purity and performance.
Description
Technical field
The invention belongs to the smelting iron and steel Technology, refer in particular to the production method of esr slag steel.
Background technology
As everybody knows: refine " good steel ", must refine " good slag ", slag is an important step of process for making, is used for reducing the content of harmful elements such as steel S, P, carries out molten steel and purifies, and improves steel product quality.Esr is common smelting iron and steel Technology, be used for the production of high standard (high-performance) steel, its main points are: the metal electrode bar (crude steel) that electric furnace (or electric furnace+external refining, or electric furnace+vacuum induction furnace) is smelted, carry out esr, be smelted into electroslag (esr) steel ingot.
Along with sophisticated technology is more and more higher to the performance requriements of steel, to harmful element in the steel [S], [P] control strictness further.At present, (quantity of slag generally is the heavy 4-5% of electroslag ingot to the slag that generally uses of metallurgy industry electroslag remelting technique; Its objective is that steel melts in the high-temperature alkaline slag, steel molten drops in when falling in the slag and melt cinder carries out chemical reaction Ca
+ 2+ [S] reduces S content in the steel, improves the clarity of molten steel) be to have: the binary slag system, as: CaF
2+ Al
2O
3The ternary slag system, as: CaF
2+ Al
2O
3, CaF
2+ Al
2O
3+ Mgo, CaF
2+ MgO+CaO, CaF
2+ Al
2O
3+ CaO; Polynary slag system is as CaF
2+ Al
2O
3+ CaO+MgO, CaF
2+ Al
2O
3+ CaO+MgO+TiO etc.; The proportioning of its each constituent element (ratio) also is variation.The melting technology parameter: current control is at 32-48 (A/cm) d electrode diameter, and voltage control is at (0.4-0.6) D crystallizer diameter+(26-37).
Production practice show: above-mentioned slag system adopts high temperature sludge liquid usually, and desulfuration is effective; But can only desulfurization and cleaning molten steel, can not dephosphorization; Its reason is: (1) slag system fusing point height, and liquid slag temperature height can not dephosphorization; (2) the slag system dephosphorizing capacity is poor.
The electroslag remelting dephosphorizing method of steel adopts CaO-CaF mostly
2-FeO or in above-mentioned binary, ternary slag system, add BaO or BaCO
3, BaCl
2, FeO etc., but dephosphorization effect is bad.
Summary of the invention
The object of the present invention is to provide a kind of production method of low-phosphor electroslag melt steel, adopt new high basicity slag system and electric remelting processing technology, reduce the content of harmful element in the steel [S] [P] significantly, particularly require low material and other smelting technologyes can't meet the requirements of steel grade to phosphorus, reduce the impurity element of steel, improve the performance of steel comprehensively, satisfy material purity requirement.
Technical scheme of the present invention is:
The production method of low-phosphor electroslag melt steel, it comprises the steps:
1) prepare before the refining:
Metal electrode: metal electrode bar is the electrode bar that adopts refining furnace or electric furnace+external refining cast; Dummy electrode: two end faces of dummy electrode are smooth, material: 45 steel;
Slag charge: slag charge comprises fluorite and active lime;
The striking agent, CaF
2: TiO
2=1: (1～2) or carbon dioxide process carbon electrode, drying;
2) electroslag furnace is smelted:
A. the direct starting the arc slag making of metal electrode is adopted in starting the arc slag making, comes arc to add slag rapidly, guarantees current stabilization; Slag charge adds the back and promoted electric current in 5～15 minutes, is controlled at prescribed value;
Voltage when the voltage during slag making is electroslag smelting, electric current is no more than 6000A;
B. esr
Slag system and proportioning: CaO: CaF
2=(15～25%): (75～85%);
Electrode size=0.4-0.7D crystallizer diameter;
The quantity of slag=4-5%G, the G ESR ingot is heavy;
C. smelting operation when the slag charge fusing is over, after electric current is raised to prescribed value, changes normal smelting over to; Electric current, the lower limit of voltage control when conventional electroslag smelting;
D. smelt the later stage filling, placement method: fall electric current gradually, fall electric current 500-1000A at every turn, adopt to be interrupted and give the electric current filling;
E. electroslag ingot slow cooling: the slow cooling time was controlled at 20-60 minute.
Further, fluorite CaF
2Chemical ingredients: CaF
2〉=96%, SiO
2≤ 2%, MnO≤0.2%, H
2O≤0.3%, Pb≤0.001%, FeO≤0.2%, P≤0.03% and inevitable impurity, by weight percentage; Active lime, CaO: the preceding oven dry of active lime, moisture≤0.2%.
During esr, electric current=32-48A/cm, D electrode diameter; Voltage: 45-65V; Electric current: 2500～15000A; The quantity of slag: 7～200kg; Molten speed: 2～10 kg/minute;
In addition, the dephosphorized slag of esr steel-making of the present invention, its composition weight percent is CaF
2: CaO=75～85: 25～15.
Wherein, CaF
2The chemical ingredients of fluorite is: CaF
2〉=96%, SiO
2≤ 2%, MnO≤0.2%, H
2O≤0.3%, Pb≤0.001%, FeO≤0.2%, P≤0.03% and inevitable impurity, by weight percentage.
Moisture≤0.2% of the active lime of CaO.
The dephosphorized slag of the esr steel-making of the present invention's design is CaF
2+ CaO binary slag is mixed by fluorite and active lime; This binary slag melting point lower (during esr, electric current and the voltage control lower limit when conventional electroslag smelting just can make solid slagization) is the low temperature liquid slag, helps dephosphorization (high-temperature liquid state slag, dephosphorization difficulty);
During esr steel-making, should adopt the protective atmosphere electroslag furnace.This be because: the easy moisture absorption of CaO is wet in this slag system, bad keeping; And air-breathing serious during melting, electroslag melt steel easily produces subsurface bubble, influences the quality of steel.
CaF
2, CaO binary high basicity slag, can effectively remove the harmful element of electroslag melt steel, its principle is: during esr steel-making, the electrode of steel melts in molten slag, the molten steel molten drop carries out chemical reaction by high basicity slag liquid in dropping process, sulphur in the removal steel and phosphorus are removed silicon, the manganese in the steel simultaneously; Chemical equation: 2[P]+3Ca=Ca
3P
2, Ca
+ 2+ [S]=CaS, O
-2+ 2[Si]=SiO
2, [Mn]+O
-2=MnO; Purification superelevation Clean Steel, effect is remarkable.
Adopt the dephosphorized slag of above-mentioned esr steel-making to be used for the production method of low-phosphor electroslag melt steel, in: adopt prepare before smelting, electroslag furnace two stages of smelting, produce sulphur, the phosphorus removal effect is good, the high-quality electroslag melt steel that clarity is high.Key points for operation: prepared electrode and dummy electrode are welded; The striking agent is placed on heelpiece center, puts into crystallizer and installs; Install metal electrode and striking agent and align the back to electricity, the electrode that descends at a slow speed comes arc to add the slag charge that oven dry mixes, and when the slag charge fusing is over, after electric current is raised to prescribed value, changes normal smelting over to; Filling before finishing.
Fs, prepare before smelting:
Metal electrode is prepared: common process, metal electrode bar are the electrode bars that adopts refining furnace or electric furnace+external refining cast;
Dummy electrode is prepared: common process, and two end faces of dummy electrode are necessarily smooth, and electrode bar welds, and weldering is straight, and weld is rubescent when being strictly on guard against smelting comes off with electrode bar; 800 millimeter 90 of the specification of dummy electrode: Φ～, length 500～2000m; The material of dummy electrode: 45 steel;
The preparation of slag charge: slag charge is made up of fluorite and two kinds of materials of active lime; The chemical ingredients of fluorite should meet following regulation: CaF
2〉=96%, SiO
2≤ 2%, MnO≤0.2%, H
2O≤0.3%, Pb≤0.001%, FeO≤0.2%, P≤0.03%; Active lime (CaO): the preceding oven dry of active lime, moisture must be≤0.2%;
The preparation of heelpiece: common process, with the heelpiece of steel grade or approximate steel grade; Require the heelpiece two sides smooth, no flash contacts one side with the water-cooled heelpiece, polish with emery wheel, and being forbidden has rust, guarantees that heelpiece and water-cooled seated connection touch closely, and conduction is good; Specification, 130～10000 millimeters of heelpiece diameter: Φ, heelpiece thickness: 15～30 millimeters.
Striking agent (CaF
2: TiO
2=1: 1～2 or carbon dioxide process carbon electrode) preparation: common process, the striking agent must be dry.
Subordinate phase, electroslag furnace are smelted (starting the arc slag making → electroslag furnace normally smelts → filling → electroslag ingot take off slow cooling behind the ingot):
(1) starting the arc slagging process: common process technology; Adopt the direct starting the arc slag making of metal electrode: metal electrode and striking agent align; Give electricity, electrode descends at a slow speed; Come arc to add slag rapidly, guarantee that electric current is very fast stable.Slag charge adds the back and promoted electric current in 5～15 minutes, is controlled at prescribed value.Voltage when the voltage during slag making is electroslag smelting, electric current generally are no more than 6000A.
(2) electroslag remelting process parameter
Slag system and proportioning: CaO: CaF
2=(15～25%): (75～85%)
The setting of parameter: electrode size=0.4-0.7D crystallizer diameter;
CaO, CaF
2Through high bake (baking to slag charge is strict), remove moisture and crystal water;
The quantity of slag=4-5%G (ESR ingot is heavy);
Electric current=32-48 (A/cm) D electrode diameter generally is controlled at lower limit;
The lower limit of voltage control when conventional electroslag melting.
Voltage: 45-65V; Electric current: 2500～15000A.
The quantity of slag: 7～200kg.
Molten speed: 2～10 kg/minute
(3) smelting operation
When the slag charge fusing is over, after electric current is raised to conventional prescribed value, change normal smelting over to; Electric current, the lower limit of voltage control when conventional electroslag smelting.
(4) smelt the later stage filling
Placement method: fall electric current gradually,, can adopt to be interrupted and give the electric current filling at every turn with electric current 500-1000A.
Filling effect: filling must be fully, and the whole no recessed heart is held in filling level with both hands.
(5) slow cooling of electroslag ingot and sampling, the slow cooling of electroslag ingot: the slow cooling time was controlled at 20-60 minute.
The chemical ingredients sampling: sampling is directly to drill through on electroslag ingot.Specimen shape requires small shreds, and weight all is not less than 40 grams, and sample requires cleaning, no greasy dirt, free from dust, no bits.
The present invention designs a kind of esr (CaF
2+ CaO) binary slag system and new Technology is used for the esr of steel, this binary slag system have the melt cinder temperature low, solidify fast characteristics, its dephosphorization principle may be: CaO (Gu) → Ca (Gu)+O
2(gas), 3Ca+2[P] → Ca
3P
2, 2[P]+5[O]+3 (CaO)=Ca
3P
2O
5, Ca
+ 2+ [S]=CaS, O
-2+ 2[Si]=SiO
2, [Mn]+O
-2=MnO promptly in the harmful element content such as [S], [Si], [Mn], reduces the content of harmful element [P] in the steel in reducing steel, dephosphorization efficient is more than 50%, and desulfurization is more than 60%, and silicomanganese also reduces.Technology of the present invention is simple, this binary slag system low cost of manufacture, and under the prerequisite that does not improve electroslag steel cost, dephosphorization desulfuration effect is remarkable, improves the purity of tissue, homogeneity of ingredients and the raising steel of steel greatly, improves the performance and the quality of steel.
Advantage of the present invention is,
The present invention can reduce the content of harmful element in the steel [S], [P] significantly, reduce the content of silicomanganese in the steel simultaneously, improve the clarity of molten steel, pure iron takes off [P] rate more than 50%, [S] rate of taking off more than 50%, SiMn reduces, take off [S], [P] effect is remarkable, improve tissue, the homogeneity of ingredients of steel greatly, improve the performance and the quality of steel; The electroslag dephosphorizing technology is domestic still for the first time, and [P] takes off in China in the electroslag metallurgy field blank has been filled up in this invention; Significant to the purity that improves the superelevation Clean Steel, as application such as ultrahigh-strength steel, senior ultra pure iron, shortened the distance of China simultaneously greatly with world developed country metallurgical material level.
The present invention is that the steel grade that the thiophos silicomanganese all limits has meaning to maraging steel, secondary hardened steel, and it is more meaningful to require lower steel grade and other method phosphorus can not be controlled lower steel such as stainless steel etc. to phosphorus especially; Can also be used for maraging steel, secondary hardened steel, high-class stainless steel high-quality raw material, also can be used for the electroslag melting of low phosphoretic steel.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Referring to Fig. 1, technical process of the present invention comprise prepare before smelting, electroslag furnace smelts, promptly starting the arc slag making → electroslag furnace normally smelt → filling → electroslag ingot takes off slow cooling behind the ingot.
Example 1. pure iron take off [P] technological test
1. starting material: the metal electrode bar of electric furnace or electric furnace+external refining cast.
1.1 electrode bar chemical ingredients (%)
C?0.287、Mn?0.02、Si?0.01、S?0.007、P?0.003
200 millimeters of 1.2 electrode size: Φ, 600 kilograms of weight, 2.
1.3 heelpiece: adopt with the steel grade heelpiece 300 * 20 millimeters of heelpiece size Φ.
1.4 striking agent: carbon dioxide process carbon electrode 300g.
2. electroslag remelting process
2.1 slag system
CaO∶CaF
2＝15％∶85％
The quantity of slag: 50 kilograms
Electric current: 6000～6500A, voltage: 58V
2.2 400 millimeters of crystallizer size: Φ
3. electroslag ingot
3.1 electroslag ingot chemical ingredients (%)
C?0.095、Mn?0.015、Si?0.01、S?0.003、P?0.001
3.2 400 millimeters * 1.2m of steel ingot size: Φ; Weight: 1200 kilograms
4. take off [P] effect:
Take off [P] rate=([P] preceding-[P] back)/[P] preceding * 100%
＝(0.003％-0.001％)/0.003％×100％＝66.67％
Example 2. soft steel take off [P] technological test
1. starting material: the electrode bar of vacuum induction furnace cast.
1.1 electrode bar chemical ingredients (%)
C?0.17、Mn?0.03、Si?0.03、S?0.007、P?0.003
80 millimeters of 1.2 size: Φ, 70 kilograms of weight, 3.
1.3 heelpiece: adopt with the steel grade heelpiece 130 * 15 millimeters of heelpiece size Φ.
1.4 striking agent: carbon dioxide process carbon electrode 100g.
2 electroslag remelting process
2.1 slag system
CaO∶CaF
2＝20％∶80％
The quantity of slag: 10 kilograms
Electric current: 2500～3000A, voltage: 54-56V
2.2 165 millimeters of crystallizer size: Φ
3 electroslag ingots
3.1 electroslag ingot chemical ingredients (%)
C?0.135、Mn?0.03、Si?0.01、S?0.001、P?0.001
3.2 165 millimeters * 1.2m of steel ingot size: Φ; Weight: 200 kilograms
4 take off [P] effect
Take off [P] rate=([P] preceding-[P] back)/[P] preceding * 100%
＝(0.003％-0.001％)/0.003％×100％＝66.67％
Example 3. Ultra-low carbon high purity irons take off [P] technological test
1. starting material: the metal electrode bar of electric furnace or electric furnace+external refining cast.
1.1 electrode bar chemical ingredients (%)
C?0.008、Mn?0.06、Si?0.04、S?0.002、P?0.006
250 millimeters of 1.2 size: Φ, 560 kilograms of weight, 2.
1.3 heelpiece: adopt with the steel grade heelpiece 300 * 20 millimeters of heelpiece size Φ.
1.4 striking agent: carbon dioxide process carbon electrode 300g.
2. electroslag remelting process
2.1 slag system
CaO∶CaF
2＝25％∶75％
The quantity of slag: 52 kilograms
Electric current: 5500～6000A, voltage: 57～60V
2.2 400 millimeters of crystallizer size: Φ
3. electroslag ingot
3.1 electroslag ingot chemical ingredients (%)
C?0.006、Mn?0.02、Si?0.02、S＜0.001、P?0.002
3.2 400 millimeters * 1.3m of steel ingot size: Φ; Weight: 1100 kilograms
4. take off [P] effect
Take off [P] rate=([P] preceding-[P] back)/[P] preceding * 100%
＝(0.006％-0.002％)/0.006％×100％＝66.67％
Example 4. gas shield electroslag furnaces take off [P] technological test
1. starting material: the metal electrode bar of vacuum induction furnace cast.
1.1 electrode bar chemical ingredients (%)
C?0.17、Mn?0.04、Si?0.03、S?0.007、P?0.003
290 millimeters of 1.2 size: Φ, 1300 kilograms of weight, 1.
1.3 heelpiece: adopt with the steel grade heelpiece 300 * 20 millimeters of heelpiece size Φ.
1.4 striking agent: carbon dioxide process carbon electrode 300g.
2. electroslag remelting process
2.1 slag system
CaO∶CaF
2＝20％∶80％
The quantity of slag: 56 kilograms
Electric current: 6300～6500A voltage: 56～62V
2.2 400 millimeters of crystallizer size: Φ
3. electroslag ingot
3.1 electroslag ingot chemical ingredients (%)
C?0.12、Mn?0.026、Si?0.01、S?0.002、P?0.001
3.2 400 millimeters * 1.5m of steel ingot size: Φ; Weight: 1200 kilograms
4. take off [P] effect
Take off [P] rate=([P] preceding-[P] back)/[P] preceding * 100%
＝(0.003％-0.001％)/0.003％×100％＝66.67％
Example 5. gas shield electroslag furnaces take off [P] technological test
1. starting material: the metal electrode bar of vacuum induction furnace cast.
1.1 electrode bar chemical ingredients (%)
C?0.02、Mn?0.16、Si?0.09、S?0.010、P?0.02
290 millimeters of 1.2 size: Φ, 1300 kilograms of weight, 2.
1.3 heelpiece: adopt with the steel grade heelpiece 300 * 20 millimeters of heelpiece size Φ.
1.4 striking agent: carbon dioxide process carbon electrode 300g.
2. electroslag remelting process
2.1 slag system
CaO∶CaF
2＝20％∶80％
The quantity of slag: 55 kilograms
Electric current: 6800～7500A voltage: 57～60V
2.2 400 millimeters of crystallizer size: Φ
3. electroslag ingot
3.1 electroslag ingot chemical ingredients (%)
C?0.019、Mn?0.10、Si?0.06、S?0.002、P?0.01
3.2 steel ingot size: Φ 400mm * 1.5m; Weight: 1200kg
4. take off [P] effect
Take off [P] rate=([P]
Before-[P]
After)/[P]
Before* 100%
＝(0.02％-0.01％)/0.02％×100％＝50％
Claims (6)
1. the production method of low-phosphor electroslag melt steel, it comprises the steps:
1) smelt preceding the preparation:
Metal electrode: metal electrode bar is the electrode bar that adopts refining furnace or electric furnace+external refining cast; Dummy electrode;
Slag charge: slag charge comprises fluorite and active lime;
The striking agent, CaF
2: TiO
2=1: (1～2) or carbon dioxide process carbon electrode;
2) electroslag furnace is smelted:
A. the direct starting the arc slag making of metal electrode is adopted in starting the arc slag making, comes arc to add slag rapidly, guarantees current stabilization; Slag charge adds the back and promoted electric current in 5～15 minutes, is controlled at prescribed value; Voltage when the voltage during slag making is electroslag smelting, electric current is no more than 6000A;
B. esr
Slag system and proportioning: CaO: CaF
2=(15～25%): (75～85%);
Electrode size=0.4-0.7D, D crystallizer diameter;
The quantity of slag=4-5%G, the G ESR ingot is heavy;
C. smelting operation after slag charge has melted, and electric current is raised to conventional prescribed value, changes normal smelting over to; Electric current, the lower limit of voltage control when conventional electroslag smelting;
D. smelt the later stage filling, placement method: fall electric current gradually, fall electric current 500-1000A at every turn, adopt to be interrupted and give the electric current filling;
E. electroslag ingot slow cooling: the slow cooling time was controlled at 20-60 minute.
2. the production method of low-phosphor electroslag melt steel as claimed in claim 1 is characterized in that, fluorite CaF
2Chemical ingredients: CaF
2〉=96%, SiO
2≤ 2%, MnO≤0.2%, H
2O≤0.3%, Pb≤0.001%, FeO≤0.2%, P≤0.03% and inevitable impurity, by weight percentage; Active lime, CaO: the preceding oven dry of active lime, moisture≤0.2%.
3. the production method of low-phosphor electroslag melt steel as claimed in claim 1 is characterized in that, during esr, and electric current=32-48A/cm, D electrode diameter; Voltage: 45-65V; Electric current: 2500～15000A; Molten speed: 2～10 kg/minute; The quantity of slag: 7～200kg.
4. the dephosphorized slag of esr steel-making, its composition weight percent is CaF
2: CaO=75～85: 25～15.
5. the dephosphorized slag of esr steel-making as claimed in claim 4 is characterized in that CaF
2The chemical ingredients of fluorite is: CaF
2〉=96%, SiO
2≤ 2%, MnO≤0.2%, H
2O≤0.3%, Pb≤0.001%, FeO≤0.2%, P≤0.03% and inevitable impurity, by weight percentage.
6. the dephosphorized slag of esr steel-making as claimed in claim 4 is characterized in that, moisture≤0.2% of the active lime of CaO.
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| CN102925712A (en) * | 2012-11-23 | 2013-02-13 | 重庆材料研究院 | Electroslag remelting method for difficult-processing high alloy stainless steel and electroslag remelting slag system adopting electroslag remelting method |
| CN103333993A (en) * | 2013-07-11 | 2013-10-02 | 武汉钢铁(集团)公司 | Dephosphorizing method of vacuum induction furnace |
| CN104745831A (en) * | 2013-12-30 | 2015-07-01 | 大冶特殊钢股份有限公司 | Carbon conductive slag for electroslag steel smelting |
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