CN101660021B - Method for desulfurizing ultra-low carbon pure steel in circulating vacuum degassing method - Google Patents
Method for desulfurizing ultra-low carbon pure steel in circulating vacuum degassing method Download PDFInfo
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- CN101660021B CN101660021B CN2009100755104A CN200910075510A CN101660021B CN 101660021 B CN101660021 B CN 101660021B CN 2009100755104 A CN2009100755104 A CN 2009100755104A CN 200910075510 A CN200910075510 A CN 200910075510A CN 101660021 B CN101660021 B CN 101660021B
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Abstract
A method for desulfurizing ultra-low carbon pure steel in a circulating vacuum degassing method comprises the following steps: 1. molten iron pretreatment desulfurization: blast-furnace molten iron is desulfurized by injecting and blowing granular magnesium, and slag skimming is carried out after desulfurization to skim most desulfurized slag; 2. decarbonization and dephosphorization in a top and bottom combined blown converter: the desulfurized molten iron is added into the top and bottom combined blown converter to carry out converting and decarbonization and dephosphorization, when tapping, alloying is not carried out, and synthetic slag is added in the tapping process; 3. RH deep decarbonization and desulfurization: a. a ladle which is filled with poured molten steel is moved to an RH work station to carry out vacuum carbon-oxygen reaction deep decarbonization, and carbon reaches 0.001 percent to 0.0025 percent; b. after RH decarbonization is finished, aluminum deoxidation is carried out, and dissolved oxygen is not more than 0.0005 percent; and c. after the deoxidation for 2 to 3min, desulfurater is added, and low-carbon active lime is desulfurized; and 4. continuous casting. The method for desulfurizing ultra-low carbon pure steel in the circulating vacuum degassing method has low cost and high desulfurization rate.
Description
Technical field
The present invention relates to the method for a kind of Ultra-low carbon Clean Steel RH desulfurization, promptly the Ultra-low carbon Clean Steel is with the method for recirculation degassing desulfurization.
Background technology
Except that free-cutting steel, sulphur is the harmful element in the steel usually, and sulphur forms sulfide inclusion in steel, reduces the ductility and the toughness, particularly impelling strength of steel.Sulfur-bearing Gao Shihui causes steel hydrogen to induce the generation of crackle, and the resistance to corrosion of steel greatly reduces, and particularly harm is bigger concerning oil pipeline.Welding property is one of most important use properties of steel, and the welding property to steel when sulfur-bearing is high is unfavorable, when sulphur exists with the form of iron sulphide, can cause hot-shortly, significantly reduces the hot workability of steel.Therefore, improve the purity of steel, it is most important to improving steel performance and reducing defective to reduce sulphur content.
Along with the demand of domestic and international market, more and more stricter to the requirement of steel product quality, need carry out desulfurization in the RH operation in some Ultra-low carbon Clean Steel production processes and handle.The sulfur method of RH treating processes has RH blowing desulfurization pulvis and RH vacuum chamber to drop into two kinds of sweetening agents at present.RH powder injection desulphurization rate is higher, but needs the blowing device of complexity, costliness, and it is lower that the RH vacuum chamber drops into the relative desulfurization degree of sweetening agent, does not need to add, transform any equipment, and method is easy.The sweetening agent that satisfies this requirement mainly contains two big classes: a class is CaO-CaF
2Slag system serves as main the composition with lime and fluorite.This sweetening agent sweetening effectiveness is more satisfactory, but the fluorite in the component seriously corrodes RH cell body and tubular stinger refractory materials, goes back contaminate environment simultaneously; Another kind of is CaO-Al
2O
3One SiO
2Slag system serves as main the composition with lime and aluminium vanadine, melts into calcium aluminate through electric furnace, its fusing point reduces greatly, and slagging speed is fast when being used for the RH desulfurization, corrodes very little to the anti-material of vacuum trough body, but this class sweetening agent is through the electric furnace fusion, carbon containing is higher, is unsuitable for smelting suprelow carbon steel, and the calcium aluminate of fritting simultaneously basicity is very low, lime wherein is after fusion, reactive behavior descends, and also need add lime again in the RH sweetening process, and desulphurization cost is higher.
Summary of the invention
In order to overcome the above-mentioned deficiency of existing Ultra-low carbon Clean Steel, the invention provides a kind of cost is low, desulfurization degree is high Ultra-low carbon Clean Steel method with the recirculation degassing desulfurization with the method for recirculation degassing desulfurization.
This Ultra-low carbon Clean Steel comprises following sequential steps with the method for molten steel recirculation degassing desulfurization:
(1) molten iron pretreatment desulfurizing
Adopt winding-up particle magnesium to blast-melted desulfurization, molten iron per ton adds 0.4～0.5kg particle magnesium, the quality percentage composition of sulphur reaches 0.001%～0.005% after the desulfurization, skims after the desulfurization to handle to remove most of desulfurization slag, and the amount of removing is no less than 90% of desulfurization slag quality.
(2) top and bottom combined blown converter decarburization, dephosphorization
Desulfurized molten iron is added top and bottom combined blown converter blow, carry out the decarburization dephosphorization treatment, the per distribution ratio of the quality of molten steel composition and temperature reach the pushing off the slag tapping of following requirement back:
C 0.02％～0.05％Si≤0.02％Mn 0.01％～0.10％P≤0.008％
S≤0.006％[O]：0.07～0.09％0.0008％≤N≤0.003％
All the other are Fe and unavoidable impurities.Liquid steel temperature is not less than 1680 ℃.
Do not carry out alloying during tapping, tapping process adds synthetic slag, and synthetic slag adds in the ladle with steel stream in tapping process.(added synthetic slag composition: CaO:40～60%, Al
2O
3: 20～50%, MgO:5～15%, SiO
2≤ 5%) add-on of synthetic slag is that molten steel per ton adds 2～6kg, and changing slag is CaO-SiO
2-Al
2O
3Slag system.
(3) the dark decarburization of RH, desulfurization
A will pour the ladle of molten steel into and transport to the RH station, and liquid steel temperature is not less than 1600 ℃, carry out under the vacuum oxidation of coal carbonization treatment deeply, and carbon is taken off to 0.001%～0.0025%, and decarburization finishes.In carbon rejection process, when liquid steel temperature is lower than 1600 ℃, add the aluminium heating by O2 blowing, dark carbonization treatment time 16～24min is generally 20min, and the vacuum tightness during dark decarburization is 50～150Pa, is generally 100Pa.
Carry out aluminum deoxidation after b RH decarburization finishes, molten steel aluminium add-on per ton is 0.7kg～2kg, and during deoxidation, liquid steel temperature is not less than 1560 ℃, and vacuum tightness 67Pa～200Pa takes off dissolved oxygen and is not more than 0.0005%, and deoxidation finishes;
The c deoxidation finishes low-carbon active lime (C≤0.02% that 2～3min adds sweetening agent granularity 5～8mm, CaO 〉=90%), molten steel add-on per ton is 2～8kg, low-carbon active lime adds to adopt continuously and evenly adds, low-carbon active lime adds the back molten steel and keeps high vacuum, 5～10min is stirred in circulation under vacuum tightness 67pa～100pa, and the molten steel face forms low melting point CaO-Al in the RH vacuum chamber
2O
3Slag system carries out desulfurization.Handle through desulfurization, sulphur content is reduced to 0.0015～0.0050% in the steel, and desulfurization degree reaches 30～50%, has satisfied the requirement of Ultra-low carbon Clean Steel low sulfur content.
But above-mentioned molten steel continuous casting or be molded into steel ingot.
(4) continuous casting
Ladle hangs continuous casting working procedure and carries out continuous casting, and continuous casting adopts the cast of argon gas whole process protection.
This Ultra-low carbon Clean Steel is with the method for molten steel recirculation degassing desulfurization, and desulfurization degree reaches 30～50%, can not cause molten steel carburetting simultaneously, has satisfied the requirement of Ultra-low carbon Clean Steel low sulfur content; The RH sweetening process does not adopt CaF
2, the not carburetting of sweetening process molten steel has reduced simultaneously to the erosion of tubular stinger and to the pollution of environment; Reduced the RH desulphurization cost.
Embodiment
Describe the embodiment of Ultra-low carbon Clean Steel RH sulfur method of the present invention in detail below in conjunction with embodiment, but the embodiment of this Ultra-low carbon Clean Steel sulfur method is not limited to following embodiment.
Embodiment one
Present embodiment is to produce ultra low carbon IF steel, 195 tons of actual treatment amounts with 180 tons of converters+RH refining furnace.
The quality per distribution ratio of the composition of the ultra low-carbon steel IF steel that present embodiment is smelted is:
C?0.0022％ Si?0.02％ Mn?0.15％
P?0.008％ S 0.0036％ Al?0.04％ N?0.0025％
All the other are Fe and unavoidable impurities.
The steps in sequence of present embodiment is: 180 tons of molten iron pretreatment desulfurizing → 180 ton top and bottom combined blown converter decarburizations, the dark decarburization of dephosphorization → 180 ton RH, desulfurization, deoxidation → continuous casting.
The concrete steps of present embodiment are as follows successively:
(1) molten iron pretreatment desulfurizing
Adopt winding-up particle magnesium 85kg desulfurization, sulphur content reaches 0.0025% after the desulfurization, skims after the desulfurization to handle to remove most of desulfurization slag, removes 90% separation of flow slag.
(2) top and bottom combined blown converter decarburization, dephosphorization
Desulfurized molten iron is added top and bottom combined blown converter blow, carry out the decarburization dephosphorization treatment, the composition of molten steel and temperature reach the pushing off the slag tapping of following requirement back:
C?0.026％ Si?0.02％ Mn?0.08％ P?0.006％
S?0.0058％ [O]：0.08％ N?0.0025％
All the other are Fe and unavoidable impurities.1685 ℃ of liquid steel temperatures.
Do not carry out alloying during tapping, tapping process adds synthetic slag 600kg and carries out the slag adjustment, changes the slag slag system.
(3) the dark decarburization of RH, desulfurization
A will pour the ladle of molten steel into and transport to the RH station, and 1620 ℃ of liquid steel temperatures carry out the dark carbonization treatment of reaction between carbon and oxygen under the vacuum, and carbon is taken off to 0.002%, and decarburization finishes.In carbon rejection process, liquid steel temperature is not less than 1600 ℃, dark carbonization treatment time 20min, and the vacuum tightness during dark decarburization is 100Pa.
B RH decarburization is carried out aluminum deoxidation after finishing, and (wherein having 150kg aluminium to enter molten steel becomes alloying element, and aluminium content is in the molten steel: Al:0.02%～0.06%) to add aluminium 580kg.During deoxidation, 1565 ℃ of liquid steel temperatures, vacuum tightness 80Pa takes off the dissolved oxygen in the steel to 0.0003% (3ppm), and deoxidation finishes;
The c deoxidation finishes low-carbon active lime (C≤0.02% that 3min adds sweetening agent granularity 5～8mm, CaO 〉=90%) 850kg, sweetening agent lime adds to adopt continuously and evenly adds, sweetening agent adds the back molten steel and keeps high vacuum, 8min is stirred in circulation under vacuum tightness 80pa, be reduced to 0.0036% through handling sulphur content in the steel by original 0.0058%, desulfurization degree reaches 37.9%, satisfied the requirement of ultra low-carbon steel IF steel low sulfur content, sampling analysis carbon content of molten steel before and after the desulfurization, be respectively 0.0021%, 0.0022%, basic not variation.
(4) continuous casting
Continuous casting adopts the cast of argon gas whole process protection, casts the high slab of the wide 230mm of the long 1580mm of 12000mm.
Embodiment two
Present embodiment is that real treatment capacity is 190 tons with 180 tons of converters+RH refining furnace smelting ferroferrite.
The quality per distribution ratio of the composition of the ultra low-carbon steel pure iron that present embodiment is smelted is:
C?0.0022％ Si?0.04％ Mn?0.06％
P?0.008％ S 0.0043％ Al?0.040％ N?0.0022％
All the other are Fe and unavoidable impurities.
The steps in sequence of present embodiment is: 180 tons of molten iron pretreatment desulfurizing → 180 ton top and bottom combined blown converter decarburizations, the dark decarburization of dephosphorization → 180 ton RH, desulfurization → continuous casting.
The concrete steps of present embodiment are as follows successively:
(1) molten iron pretreatment desulfurizing
Adopt winding-up particle magnesium 90kg desulfurization, sulphur content reaches 0.002% after the desulfurization, skims after the desulfurization to handle to remove most of desulfurization slag, removes 90% separation of flow slag.
(2) top and bottom combined blown converter decarburization, dephosphorization
Desulfurized molten iron is added top and bottom combined blown converter blow, carry out the decarburization dephosphorization treatment, the composition of molten steel and temperature reach the pushing off the slag tapping of following requirement back:
C?0.024％ Si?0.016％ Mn?0.06％ P?0.008％ S?0.006％
[0]：0.08％ N 0.0026％
All the other are Fe and unavoidable impurities.1690 ℃ of liquid steel temperatures
Do not carry out alloying during tapping, tapping process adds synthetic slag 600kg and carries out the slag adjustment, changes the slag slag system.
(3) the dark decarburization of RH, desulfurization
A will pour the ladle of molten steel into and transport to the RH station, and liquid steel temperature is not less than 1630 ℃, carry out the dark carbonization treatment of reaction between carbon and oxygen under the vacuum, and carbon is taken off to 0.0015%, and decarburization finishes.Begin in decarburization, liquid steel temperature is not less than 1600 ℃, and the vacuum tightness during dark decarburization is 80Pa.
B RH decarburization is carried out aluminum deoxidation after finishing, and adds aluminium 480kg (wherein having 150kg aluminium to enter molten steel becomes alloying element, aluminium content Al≤0.06% in the molten steel).During deoxidation, 1570 ℃ of liquid steel temperatures, vacuum tightness 80Pa takes off the dissolved oxygen in the steel to 0.0002% (2ppm) deoxidation and finishes;
The c deoxidation finishes 2min and adds sweetening agent low-carbon active lime (C≤0.02%, CaO 〉=90%) 780kg, sweetening agent lime adds to adopt continuously and evenly adds, sweetening agent adds the back molten steel and keeps high vacuum, 10min is stirred in circulation under vacuum tightness 80pa, be reduced to 0.0043% through handling sulphur content in the steel by original 0.0062%, desulfurization degree reaches 30.6%, satisfied the requirement of ultra low-carbon steel IF steel low sulfur content, sampling analysis carbon content of molten steel before and after the desulfurization, be respectively 0.0022%, 0.0022%, do not change.
(4) continuous casting
Continuous casting adopts the cast of argon gas whole process protection, casts the high slab of the wide 230mm of the long 1580mm of 12000mm.
Embodiment three
Present embodiment is to produce ultra low carbon IF steel with 80 tons of converters+RH refining furnace, and treatment capacity is 82 tons.
The quality per distribution ratio of the composition of the ultra low-carbon steel IF steel that present embodiment is smelted is
C?0.0022％ Si?0.02％ Mn?0.16％
P?0.008％ S 0.0040％ Al?0.04％ N?0.003％
All the other are Fe and unavoidable impurities.
The steps in sequence of present embodiment is: 80 tons of molten iron pretreatment desulfurizing → 80 ton top and bottom combined blown converter decarburizations, the dark decarburization of dephosphorization → 80 ton RH, desulfurization → continuous casting.
(1) molten iron pretreatment desulfurizing
Adopt winding-up particle magnesium 40kg desulfurization, sulphur content reaches 0.003% after the desulfurization, skims after the desulfurization to handle to remove most of desulfurization slag, removes 90% separation of flow slag.
(2) top and bottom combined blown converter decarburization, dephosphorization
Desulfurized molten iron is added top and bottom combined blown converter blow, carry out the decarburization dephosphorization treatment, composition and temperature reach the pushing off the slag tapping of following requirement back:
C?0.025％ Si 0.014％ Mn?0.07％ P?0.006％
S?0.0059％ [O]：0.08％ N 0.0024
All the other are Fe and unavoidable impurities.1700 ℃ of liquid steel temperatures
Do not carry out alloying during tapping, tapping process adds synthetic slag 300kg and carries out the slag adjustment, changes the slag slag system.
(3) the dark decarburization of RH, desulfurization
A will pour the ladle of molten steel into and transport to the RH station, and 1630 ℃ of liquid steel temperatures carry out the dark carbonization treatment of reaction between carbon and oxygen under the vacuum, and carbon is taken off to 0.0015%, and decarburization finishes.Begin in decarburization, find that liquid steel temperature is lower than 1600 ℃, add aluminium oxygen blast molten steel and be warmed up to 1620 ℃, dark carbonization treatment time 18min, the vacuum tightness during dark decarburization is 80Pa.
B RH decarburization is carried out aluminum deoxidation after finishing, adding aluminium 182kg (wherein has 45kg aluminium to enter molten steel and becomes alloying element, aluminium content is in the molten steel: Al:0.02%～0.06%), during deoxidation, 1560 ℃ of liquid steel temperatures, vacuum tightness 100Pa takes off the dissolved oxygen in the molten steel to 0.0002% (2ppm), and deoxidation finishes;
The c deoxidation finishes 3min and adds sweetening agent low-carbon active lime (C≤0.02%, CaO 〉=90%) 460kg, sweetening agent lime adds to adopt continuously and evenly adds, sweetening agent adds the back molten steel and keeps high vacuum, 5min is stirred in circulation under vacuum tightness 80pa, be reduced to 0.0040% through handling sulphur content in the steel by original 0.0059%, desulfurization degree reaches 32.2%, satisfied the requirement of ultra low-carbon steel IF steel low sulfur content, sampling analysis carbon content of molten steel before and after the desulfurization, be respectively 0.0023%, 0.0022%, basic not variation.
(4) continuous casting
Continuous casting adopts the cast of argon gas whole process protection, casts the high slab of the wide 220mm of the long 1280mm of 10000mm.
Explanation
Per distribution ratio in the 1-present specification all is quality per distribution ratios.
2-IF steel (Interstitial Free Steel) is a gapless atomic steel, be at Ultra-low carbon, nitrogen steel (general requirement C≤0.005%, N≤0.004%) adds a certain amount of titanium, niobium alloy element in, make carbon in the steel, nitrogen-atoms be fixed to carbide, nitride, and the steel grade that gap-free atom exists in the steel.
3-is when the decarburization of step (two) top and bottom combined blown converter, dephosphorization, and composition is an occurrence during three embodiment converter tappings, but unit have small fluctuation during converter tapping.
Claims (2)
1. a Ultra-low carbon Clean Steel is with the method for recirculation degassing desulfurization, and it comprises following sequential steps:
(1) molten iron pretreatment desulfurizing
Adopt winding-up particle magnesium to blast-melted desulfurization, molten iron per ton adds 0.4～0.5kg particle magnesium, the quality percentage composition of sulphur reaches 0.001%～0.005% after the desulfurization, skims after the desulfurization to handle to remove most of desulfurization slag, and the amount of removing is no less than 90% of desulfurization slag quality;
(2) top and bottom combined blown converter decarburization, dephosphorization
Desulfurized molten iron is added top and bottom combined blown converter blow, carry out the decarburization dephosphorization treatment, the per distribution ratio of the quality of molten steel composition and temperature reach the pushing off the slag tapping of following requirement back:
C 0.02％～0.05％Si≤0.02％Mn 0.01％～0.10％P≤0.008％
S≤0.006%[O]: all the other are Fe and unavoidable impurities for 0.07～0.09%0.0008%≤N≤0.003%, and liquid steel temperature is not less than 1680 ℃;
Do not carry out alloying during tapping, tapping process adds synthetic slag, and synthetic slag adds in the ladle with steel stream in tapping process; The add-on of synthetic slag is that molten steel per ton adds 2～6kg, and changing slag is CaO-SiO
2-Al
2O
3Slag system;
(3) the dark decarburization of RH, desulfurization
A will pour the ladle of molten steel into and transport to the RH station, and liquid steel temperature is not less than 1600 ℃, carry out the dark carbonization treatment of reaction between carbon and oxygen under the vacuum, and carbon is taken off to 0.001%～0.0025%, and decarburization finishes; In carbon rejection process, when liquid steel temperature is lower than 1600 ℃, add the aluminium heating by O2 blowing, dark carbonization treatment time 16～24min, the vacuum tightness during dark decarburization is 50～150Pa;
Carry out aluminum deoxidation after b RH decarburization finishes, molten steel aluminium add-on per ton is 0.7kg～2kg, and during deoxidation, liquid steel temperature is not less than 1560 ℃, and vacuum tightness 67Pa～200Pa takes off dissolved oxygen and is not more than 0.0005%, and deoxidation finishes;
The c deoxidation finishes the low-carbon active lime that 2～3min adds sweetening agent granularity 5～8mm, C in the low-carbon active lime≤0.02%, CaO 〉=90%, molten steel add-on per ton is 2～8kg, low-carbon active lime adds to adopt continuously and evenly adds, low-carbon active lime adds the back molten steel and keeps high vacuum, and 5～10min is stirred in circulation under vacuum tightness 67pa～100pa, and the molten steel face forms low melting point CaO-Al in the RH vacuum chamber
2O
3Slag system carries out desulfurization; Handle through desulfurization, sulphur content is reduced to 0.0015～0.0050% in the steel.
2. Ultra-low carbon Clean Steel according to claim 1 is characterized in that with the method for recirculation degassing desulfurization: after the dark decarburization of step (three) RH, desulfurization, ladle is hung continuous casting working procedure carry out continuous casting, continuous casting adopts the cast of argon gas whole process protection.
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| CN103924038A (en) * | 2013-01-14 | 2014-07-16 | 宝山钢铁股份有限公司 | Desulfurizing agent and desulfurizing method for vacuum circulation refining production of ultra-low sulfur steel |
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