CN101319258A - Technique for preparing fine oxide dispersion steel - Google Patents
Technique for preparing fine oxide dispersion steel Download PDFInfo
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- CN101319258A CN101319258A CNA200810012279XA CN200810012279A CN101319258A CN 101319258 A CN101319258 A CN 101319258A CN A200810012279X A CNA200810012279X A CN A200810012279XA CN 200810012279 A CN200810012279 A CN 200810012279A CN 101319258 A CN101319258 A CN 101319258A
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Abstract
The invention relates to an external refining technology for steel making, in particular to a process method for preparing fine oxide dispersion steel, which comprises the following steps that: i) a deoxidation product is removed, wherein, power, cored wires, compound pellets or compound spheres are fed into molten steel at an LF, RH, VD or CAS-OB station through a method of power spraying, wire feeding, pellet shooting, or direct feeding of the spheres after the molten steel is deoxidated; and ii) a dispersed oxide is generated, wherein, when the content of oxygen in the molten steel is between 0.0001 and 0.008 percent, the compound spheres, spherical cores of which are mainly beneficial oxides and expanding agents, are added into the molten steel during the refining process. The method is more effective and safer to the control of oxide inclusions in the molten steel, and can steadily and quickly perform the mass production of the fine oxide dispersion steel the oxide particle diameters of which are less than 1mu m, thereby extremely improving the quality of the steel and reducing smelting cost. The method has simple process and easy operation, and is applicable to a modern mass steel production process.
Description
Technical field
The present invention relates to a kind of furnace outer refining technology of steel-making, particularly a kind of processing method for preparing fine oxide dispersion steel belongs to metallurgical technology field.
Background technology
As everyone knows, utilize useful inclusion (CaO, the Ti of disperse in the steel
2O
3, BN, REM (O, S), VN, TiN, ZrO
2Deng) can improve steel quality.In recent years, particle diameter is less than the inclusion of 2 μ m, especially utilizes oxide based inclusion to improve that the technology of dispersive flux receives publicity in the steel.Recently some patent disclosures in order to increase the dispersive flux of oxide compound, when pre-deoxidation, oxygen level adjusted to certain limit after, add strong reductor again, this is a method of utilizing a deoxidation products.
For example in patent JP 2001-288509 document, the oxygen in the molten steel is controlled at 20～80ppm after, add Ti, Al and Ca successively and carry out deoxidation, this is to add according to deoxidizing capacity order from weak to strong, can refinement and increase the dispersed oxide amount.This method both can reduce the degree of supersaturation of steel water oxygen, can also carry out deoxygenation repeatedly, had played the effect of inhibited oxidation thing hypertrophy and thickization.But in the method that patent documentation is mentioned, the composition of inclusion is by the deoxidant element decision of adding repeatedly, and the dispersive flux of oxide compound is dissolved in oxygen decision in the molten steel by the initial stage, nor refinement and disperse that can the promotes oxidn thing.That is to say that these methods do not exceed the scope of traditional method of deoxidation, neither effectively increase the technique means of the dispersive flux of fine foreign matter.
Also there are some patent documentations to report in addition or control its composition oxygen blown method in molten steel for the dispersive flux that increases fine oxide.
In patent documentation JP8-246026, the control method of steel inclusion form is, add reductor after, oxygen blast in the molten steel of sedation, the blowing oxygen quantity of molten steel per ton is 1 * 10
-2～6 * 10
-2But in this document, the only simple interpolation oxygen source method of employing.In patent documentation JP10-193046, mention the supply method of oxygen and (used the solid oxygen ion conductor, by applying voltage, oxygen is joined in the molten steel), fine oxide generation and diffusion method and in molten steel, be blown into oxidizing gas, make the method for fine oxide dispersion.These methods are oxygen supply under hypoxia all, and degree of supersaturation is not high in deoxygenation, can suppress the generation of thick deoxidation resultant.But the method for mentioning in this document is being in the process for producing steel and iron of prerequisite with the mass production because the oxygen feed speed is slow, poor practicability.After patent documentation JP2002-256330 had mentioned and add reductor in molten steel, the molten steel that oxygen level is high was more tiny than the oxide compound in the molten steel that adds reductor.But, in this document, also mentioned the molten steel that oxygen level is high and mixed with the molten steel that adds reductor, adopt this method to be difficult to the mass production molten steel.Therefore, improve steel quality, problem demanding prompt solution is exactly stable and increases the dispersive flux of the oxide particle of disperse in steel apace, and the production method of fine oxide dispersion steel is applied in the modernized Iron and Steel Production.
Summary of the invention
The present invention be directed to that above-mentioned problems of the prior art propose, its objective is that providing a kind of is distributed in the steel the trickleer and disperse of oxide-based inclusion, improve steel product quality, be applicable in the extensive process for producing steel and iron of modernization, reach processing method at external refining process of preparing fine oxide dispersion steel.
In order to solve the problems of the technologies described above, the present invention is achieved in that the processing method of preparation fine oxide dispersion steel, may further comprise the steps: (i) removal of deoxidation products: behind steel liquid deoxidation, by dusting, line feeding, penetrating the directly method of feeding of ball or spheroid, feed pulvis, cored-wire, compound ball ball or composite sphere to molten steel at LF, RH, VD or CAS-OB; The (ii) generation of disperse oxide: when the molten steel oxygen level 0.0001%～0.008% the time, the composite sphere that the ball core is mainly useful oxide compound, swelling agent adds molten steel in the RH refining process.
Describedly feed pulvis, cored-wire, compound ball ball or composite sphere to molten steel at LF, RH, VD or CAS-OB station:
(1) pulvis: finish to spray into molten steel before back or VD refining begin in LF, RH, VD or CAS-OB refining, delivering gas is Ar, CO
2In the mixed gas of any one or the two, carry air pressure to be controlled at 0.01～2.0MPa, the pulvis feed quantity is at 0.3～1.5kg/t, the pulvis transfer rate is at 0.01～3.5kg/s.
(2) cored-wire: finish the back feeding in LF, RH, VD or CAS-OB refining later stage alloying, the line feeding process stops Argon and stirs, wire-feeding velocity is at 180～350m/min, feed quantity is at 50～800m/t, static 0.5～10min after the line feeding, carry out Argon again and gently handle, the flow of argon gas is 50～280Nl/min, and weak argon blowing time is 0.5～5min.
(3) compound ball ball: penetrate ball at LF, RH or CAS-OB refining later stage, adopt Ar, CO
2In the mixed gas of any one or the two as carrier, air pressure is controlled at 0.1～1.0MPa.The amount of injecting is 0.5～5kg/t, and feeding speed is at 0.1～3.0kg/s.
(4) composite sphere: add in the RH refining treatment later stage, the vacuum tightness of RH is at 66.7～500Pa.Adding the implantation site is the downtake place of tremie pipe offside, adds back circulation 1～15min, and feed quantity is at 0.3～1.5kg/t, and feeding speed is at 0.01～2.0kg/s.
The add-on of the described composite sphere of step I i is 0.5～3.5kg/t, and the single add-on is at 50～130kg, and adding speed is 0.1～1.5kg/s.
Described pulvis is prepared from by following raw materials by weight: low melting point pre-melted slag pulvis 1～70%, the mixture 1～60% of lime carbonate, magnesiumcarbonate or lime carbonate and magnesiumcarbonate, calcium oxide or magnesium oxide or calcium oxide and magnesian mixture 10～98%, Calcium Fluoride (Fluorspan) 0～40%, binding agent 0～20%.
Described pulvis is prepared from by following raw materials by weight: low melting point pre-melted slag pulvis 10～50%, the mixture 10～45% of lime carbonate, magnesiumcarbonate or lime carbonate and magnesiumcarbonate, calcium oxide or magnesium oxide or calcium oxide and magnesian mixture 30～70%, Calcium Fluoride (Fluorspan) 5～30%, binding agent 5～15%.
Described cored-wire is a core with above-mentioned powder, is that crust is prepared from the thick mild-carbon steel strip of 2～5mm.
Described composite sphere is to be made of ball core and shell, and described shell mainly is made of calcium oxide or magnesian one or both mixture.
Described ball core is prepared from by following raw materials by weight: useful oxide compound 0.1～99%, swelling agent 1～70%, binding agent 0～30%.
Described ball core is prepared from by following raw materials by weight: useful oxide compound 30～80%, swelling agent 8～55%, binding agent 5～15%.
Described ball core is prepared from by following raw materials by weight: low melting point pre-melted slag pulvis 1～70%, swelling agent 1～60%, Calcium Fluoride (Fluorspan) 0～40%, binding agent 0～20%.
Described ball core is prepared from by following raw materials by weight: low melting point pre-melted slag pulvis 10～50%, swelling agent 10～45%, Calcium Fluoride (Fluorspan) 5～30%, binding agent 5～15%.
The ball core of the described compound ball ball of step I, composite sphere is mainly low melting point pre-melted slag pulvis, swelling agent.
Described shell also comprises 0～20% binding agent.
Described useful oxide compound is CaO, Ti
2O
3, ZrO
2With in the rare earth oxide any one.
Described rare earth oxide is to contain in Ce, Nd, La, Gd, the Sm oxide compound any one.
Described swelling agent is made of the mixture of lime carbonate, magnesiumcarbonate or lime carbonate and magnesiumcarbonate.
Described low melting point pre-melted slag pulvis by following raw materials by weight through being prepared from: CaO 10～70%, Al
2O
315～50%, SiO
20～10%, MgO 0～10%, CaF
20～30%, its fusing point is at 1100 ℃～1550 ℃.
Described binding agent is any one or a two or more mixture in clay, Portland cement, wilkinite, the water glass.
The granularity of described raw material is at 1nm～3.5mm, wherein calcium oxide, magnesian activity 〉=200ml.
Decomposition reaction at first takes place after adding molten steel in pulvis of the present invention, cored-wire, compound ball ball or composite sphere, produces the CO of a large amount of small and disperseds
2Gas.The fierceness that reaction process itself just makes the molten steel around pulvis, cored-wire, compound ball ball or the composite sphere produce among a small circle flows and stirring, come-up condition and chance is provided for the rising of oxide inclusion.In addition, the gas that produced can rise by the polymerization bubble, and the formation of small bubbles and uphill process have been implemented stirring to molten steel among a small circle exactly.The forming process of small bubbles is exactly the process of dross inclusion adsorption, that is to say, around small bubbles, has adsorbed countless oxide inclusion, and the come-up of small bubbles also is being with oxide inclusion emersion molten steel, is discharged in the slag.Carbonate pulvis small and dispersed in the feeding molten steel, countless carbonate powders decompose in molten steel, produce dispersing gas, and aggregate into small bubbles come-ups, just form numerous Molten Steel Flow or stirring among a small circle like this in molten steel, gather, whole molten steel is all flowing, is seething with excitement, add the come-up of numerous small bubbles, make the removal of oxide inclusion more in full force and effect.Meanwhile, the mobile molten steel takes place in different zones or among a small circle in, the oxygenant that is added also makes the oxide compound come-up of generation discharge when the molten steel oxygen level is reduced.
In addition, another product C aO size of pulvis of the present invention, cored-wire, compound ball ball or composite sphere decomposition reaction is tiny, can in molten steel, melt rapidly form that slag drips and with molten steel in Al
2O
3Inclusion forms on the low melting point calcium-aluminate and floats in the ladle slag, thereby removes the Al that refining process produces
2O
3Inclusion reduces entire oxygen content in the steel content.By the optimized choice of various formulations being controlled the speed and the efficient of entire reaction.
Advantage of the present invention and beneficial effect are as follows:
The present invention is adapted to the processing method of various types of oxide dispersion steels, this method is directly to add useful oxide compound and add reactive material in molten steel in molten steel by the method for feeding pulvis of the present invention, cored-wire, compound ball ball or composite sphere in the steel-making refining process, removes the deoxidation products in the steel in the short period of time fast.Thereby the control to oxide inclusion in the molten steel is more effective and complete, and can stablize and fast the mass production oxide diameter sizes less than the fine oxide dispersion steel of 1 μ m, technology of the present invention is simple, easy handling, and cost is low, effectively is applied in the extensive process for producing steel and iron of modernization.
Embodiment
Below in conjunction with specific embodiment the present invention is further elaborated, but protection scope of the present invention is not limited by specific embodiment, is as the criterion with claims.In addition, with under the prerequisite of technical solution of the present invention, any change or change that those of ordinary skills that the present invention did are realized easily all will fall within the claim scope of the present invention.
Embodiment 1
Preparation fine oxide dispersion steel: at first finish back feeding cored-wire in LF refining later stage alloying, the line feeding process stops Argon and stirs, wire-feeding velocity is at 180～350m/min, and feed quantity is at 100～800m/t, static 0.5～10min after the line feeding, carrying out blowing argon gas then handles, the flow of argon gas is 50～280Nl/min, and weak argon blowing time is 0.5～5min, and Argon is taken out of after finishing, ladle is transported to the RH station, vacuumize, circulate only.When the molten steel oxygen level 0.0001～0.008% the time; the composite sphere that the ball core is mainly useful oxide compound, swelling agent adds molten steel; adding the implantation site is the downtake place of tremie pipe offside, and composite sphere is taken out of cast after adding back circulation 1～5min immediately, and continuous casting adopts the whole process protection cast.
The preparation of described cored-wire, the at first preparation of low melting point pre-melted slag is got CaO powder 40kg, Al by formulation ratio
2O
3Powder 35kg, SiO
2Powder 10kg, MgO powder 10kg, CaF
2Powder 5kg puts into blender and carries out even batch mixing, and fusing in the magnesia crucible, cooling grind to form the powder that particle diameter is 1nm～3.5mm then then, and its fusing point is standby at 1100～1550 ℃; Getting its particle diameter respectively by formulation ratio again is that low melting point fritting ground-slag 30kg, calcium fluoride powder 5kg, calcium oxide powder 55kg, lime carbonate 5kg, the clay 5kg of 1nm～3.5mm puts into blender and carry out even batch mixing 1～8h, the activity 〉=200ml of wherein said calcium oxide; The powder for preparing is put into 80～200 ℃ of drying plants dries, and the time is that 8～24h is the finished product pulvis; With thickness is the crust of the soft steel band of 2～5mm as cored-wire, core is to pass through the above-mentioned pulvis of oven dry on twine machine, adopt individual layer steel band lapping type system cored-wire, cored-wire system linear velocity is 8～30m/min, and the pulvis content of cored-wire is at 100～240g/m.Cored-wire is packaged into 1000～2000m/ volume, and packing will be guaranteed good seal, prevents humidity, and uses in 20 days.
The preparation of described composite sphere, its shell is mixed with by the Portland cement and the calcium oxide that contain 1%; The ball core is got Ti by formulation ratio
2O
30.1kg; Lime carbonate 70kg; Clay 29.9kg.
By the said ratio raw material that the ball core is required carry out that fragmentation rolls, the air-flow micronizer grinds, reaching particle diameter is 1nm～3.5mm, above-mentioned powder is put into blender fully mix, mixing time is 1～3h.Above-mentioned mixed raw material is dried processing in drying plant, bake out temperature is 80～150 ℃, and the time is 2～8h.Raw material after oven dry is handled adopts scrolling method to make the ball core on balling disc, and the rotating speed of balling disc is 400～1600r/min, and the control of ball core size determines that by screening the diameter that obtains the ball core is 1～40mm; Get the required powder of shell by said ratio and carry out thorough mixing in blender, calcium oxide, magnesian activity 〉=200ml, mixing time are 1～3h; The ball core and the shell material that have made are carried out compound system ball by scrolling method on balling disc, the spheroid size is controlled definite by screening, the composite sphere that makes is of a size of 20～80mm and gets final product.The above-mentioned composite sphere that makes is dried processing in drying plant, bake out temperature is 60～200 ℃, time is 10～24h, composite sphere oven dry postcooling is packed in the ultra-thin high-strength polyethylene plastics bag, every bag of substance is 10～30kg/ bag, packing will be guaranteed good seal, prevents humidity, and uses in 20 days.
Embodiment 2
The preparation fine oxide dispersion steel: ladle is transported to the RH station, vacuumize, deoxidation alloying, clean circulation, at RH refining later stage feeding cored-wire, the line feeding choice of location is in RH downtake one side, wire-feeding velocity is at 180～350m/min, feed quantity is at 100～800m/t, and be 3～10min cycling time after the line feeding; When sampling analysis molten steel oxygen level 0.0001～0.008% the time; the composite sphere that the ball core is mainly useful oxide compound, swelling agent adds molten steel; adding the implantation site is the downtake place of tremie pipe offside; composite sphere is taken out of cast after adding back circulation 1～3min immediately, and continuous casting adopts the whole process protection cast.
The preparation of described cored-wire is at first got CaO10kg, Al by formulation ratio
2O
350kg, SiO
25kg, MgO 5kg, CaF
230kg prepares low melting point fritting ground-slag method with embodiment 1; Getting particle diameter is low melting point fritting ground-slag 1kg, Calcium Fluoride (Fluorspan) 30kg, magnesiumcarbonate 40kg, the magnesium oxide 29kg that 1nm～3.5mm prepares, and its preparation pulvis technology, oven dry are handled identical with embodiment 1; With thickness is the crust of the soft steel band of 2～5mm as cored-wire, core is to pass through the above-mentioned pulvis of oven dry on twine machine, adopt individual layer steel band lapping type system cored-wire, cored-wire system linear velocity is 8～30m/min, and cored-wire pulvis content is at 100～240g/m.Cored-wire is packaged into 1000～2000m/ volume, is beneficial to direct control add-on and adding speed, and the cross section of cored-wire is circular, and packing will be guaranteed good seal, prevents humidity, and uses in 20 days.
The preparation of described composite sphere, its shell is mixed with by containing 20% clay and calcium oxide and magnesian mixture; The ball core is got CaO55kg by formulation ratio; Lime carbonate agent 44kg; Wilkinite 1kg, other is with embodiment 1, and no longer chela is stated.
Embodiment 3
The preparation fine oxide dispersion steel: behind steel liquid deoxidation, finish the back in the VD refining and spray into the finished product pulvis to molten steel, delivering gas is Ar, CO
2Both mixed gass carry air pressure to be controlled at 0.01～2.0MPa, and the pulvis feed quantity is at 0.3～1.5kg/t, and the pulvis transfer rate is taken out of at 0.01～3.5kg/s; Ladle is transported to the refining of RH station; when sampling analysis molten steel oxygen level 0.0001～0.008% the time; the composite sphere that the ball core is mainly useful oxide compound, swelling agent adds molten steel in the RH refining process; adding the implantation site is the downtake place of tremie pipe offside; spheroid is taken out of cast after adding back circulation 1～5min immediately, and continuous casting adopts the whole process protection cast.
The preparation of described pulvis is at first got CaO70kg, Al by formulation ratio
2O
315kg, SiO
23kg, MgO 2kg, CaF
210kg prepares low melting point fritting ground-slag method with embodiment 1; Getting particle diameter is that low melting point fritting ground-slag 45kg, the lime carbonate that 1nm～3.5mm prepares is put into the vertical batch mixing 2～8h that mixes with mixture 30kg, the calcium oxide of magnesiumcarbonate with the pulvis of magnesian mixture 10kg, wilkinite 10kg, water glass 5kg; Dry processing again on drying plant, bake out temperature is 80～200 ℃, and the time is that 8～24h is the finished product pulvis.Be cooled to room temperature and pack in the ultra-thin high-strength polyethylene plastics bag, moisture sealed packing 1000kg/ bag, packing will be guaranteed good seal, prevents humidity, and uses in 20 days.
The preparation of described composite sphere, its shell is mixed with by containing 15% Portland cement and calcium oxide and magnesian mixture; The ball core is got ZrO by formulation ratio
299kg; Magnesiumcarbonate 1kg, other is with embodiment 1, and no longer chela is stated.
Embodiment 4
Preparation fine oxide dispersion steel: after LF, RH or the end of CAS-OB refining later stage alloying, the compound ball ball for preparing is joined in the molten steel by penetrating ball technology, adopt argon gas as carrier simultaneously, air pressure is controlled at 0.1～1.0MPa, the amount of injecting is 0.5～5kg/t, takes out of; Ladle is transported to the refining of RH station; when sampling analysis molten steel oxygen level 0.0001～0.008% the time; the composite sphere that the ball core is mainly useful oxide compound, swelling agent adds molten steel in the RH refining process; adding the implantation site is the downtake place of tremie pipe offside; composite sphere is taken out of cast after adding back circulation 1～5min immediately, and continuous casting is poured into a mould with whole process protection.
The preparation of described composite sphere, its shell is mixed with by containing 5% clay and calcium oxide and magnesian mixture; First kind of ball core for get boron nitride 80kg by formulation ratio, by the mixture 15kg that gets lime carbonate and magnesiumcarbonate at 2: 1, clay 4kg, water glass 1kg; Second kind of ball core is for to get CaO50kg, Al earlier by formulation ratio
2O
340kg, SiO
25kg, MgO 5kg prepare low melting point fritting ground-slag, and its preparation method is got the low melting point fritting ground-slag 60kg, Calcium Fluoride (Fluorspan) 10kg, lime carbonate 20kg, the clay 10kg that prepare with embodiment 1;
By said ratio with two kinds of required raw materials of ball core carry out respectively that fragmentation rolls, the air-flow micronizer grinds, reaching particle diameter is 1nm～1.5mm, above-mentioned two kinds of ball core powders is put into blender respectively fully mix, mixing time is 1～3h; Above-mentioned two kinds of mixed raw materials are dried processing respectively in drying plant, bake out temperature is 80～110 ℃, and the time is 2～6h; Two kinds of raw materials after above-mentioned oven dry handled adopt pressing methods system ball core on ball press respectively, and it is definite that first kind of ball core size controlled by screening, and the diameter that obtains its ball core is 15～40mm; It is definite that second kind of ball core size controlled by screening, and the diameter that obtains the ball core is 0.05～15mm.Get the required powder of shell by said ratio and carry out thorough mixing in blender, calcium oxide, magnesian activity 〉=200ml, mixing time are 1～3h.The second kind of ball core and the above-mentioned shell material that have made are carried out compound pill by scrolling method on granulating disc; control definite by screening to ball ball size; the compound ball ball that makes is of a size of 0.25～20mm; the first kind of ball core and the above-mentioned shell material that will make are carried out compound system ball by scrolling method again on granulating disc; control definite by screening to the spheroid size; the composite sphere that makes is of a size of 20～80mm; at last with the compound ball ball 60～100 ℃ of oven dry; composite sphere is 60～120 ℃ of oven dry; drying time 10～18h; be cooled to room temperature they are carried out packing 10～30kg/ bag respectively, and in 20 days, use.
Embodiment 5
The preparation fine oxide dispersion steel: the above-mentioned cored-wire of feeding after the CAS-OB Alloying Treatment, the line feeding process stops Argon and stirs, and wire-feeding velocity is at 200～350m/min, and feed quantity is at 100～800m/t.Static 0.5～10min after the line feeding carries out Argon again and gently handles, and the flow of argon gas is 50～280Nl/min, and argon blowing time is taken out of at 0.5～10min, and ladle is transported to the refining of RH station.When sampling analysis molten steel oxygen level 0.0001～0.008% the time; the composite sphere that the ball core is mainly useful oxide compound, swelling agent adds molten steel; adding the implantation site is the downtake place of tremie pipe offside; composite sphere is taken out of cast after adding back circulation 1～4min immediately, and continuous casting adopts the whole process protection cast.
The preparation of described cored-wire is at first got CaO50kg, Al by formulation ratio
2O
330kg, CaF
220kg, the method for preparing low melting point fritting ground-slag is with embodiment 1; Getting particle diameter is low melting point fritting ground-slag 3kg, Calcium Fluoride (Fluorspan) 2kg, lime carbonate 10kg, magnesium oxide 85kg and the embodiment 1 same procedure finished product pulvis that 1nm～3.5mm prepares; Be the crust of the soft steel band of 2mm again with thickness as cored-wire, core for through the above-mentioned finished product pulvis of oven dry on twine machine, with embodiment 1 same procedure system cored-wire, be packaged into the 1000m/ volume, its cross section is square, use in 20 days.
The preparation of described composite sphere, its shell is mixed with by the clay and the calcium oxide that contain 8%; The ball core is got boron nitride 65kg by formulation ratio; Lime carbonate 25kg; Portland cement 2kg, wilkinite 8kg, other is with embodiment 1, and no longer chela is stated.
Embodiment 6
The preparation fine oxide dispersion steel: add the composite sphere that the goal core is mainly low melting point pre-melted slag pulvis, swelling agent in the RH refining treatment deoxidation alloying later stage, the vacuum tightness of RH is at 66.7～500Pa.Adding the implantation site is the downtake place of tremie pipe offside; cycling time was at 1～15min after composite sphere added; when sampling analysis molten steel oxygen level 0.0001～0.008% the time; the composite sphere that the ball core is mainly useful oxide compound and swelling agent adds molten steel; adding the implantation site is the downtake place of tremie pipe offside; composite sphere is taken out of cast after adding back circulation 1～3min immediately, and continuous casting adopts the whole process protection cast.
The preparation of described composite sphere, its shell is mixed with by the clay and the magnesium oxide that contain 20%; First kind of ball core by formulation ratio get rare earth oxide 70kg, by getting lime carbonate and magnesiumcarbonate mixture 20kg, clay 7kg, water glass 3kg at 1: 1; Second kind of ball core got CaO25kg, Al earlier by formulation ratio
2O
345kg, SiO
28kg, MgO 8kg, CaF
214kg prepares low melting point fritting ground-slag, and its preparation method is with embodiment 1, and getting particle diameter is low melting point fritting ground-slag 20kg, Calcium Fluoride (Fluorspan) 5kg, magnesiumcarbonate 35kg, calcium oxide 30kg, the wilkinite 10kg that 1nm～3.5mm prepares;
By said ratio with two kinds of required raw materials of ball core carry out respectively that fragmentation rolls, the air-flow micronizer grinds, reaching particle diameter is 1nm～3.5mm, above-mentioned two kinds of ball core powders is put into blender respectively fully mix, mixing time is 1～3h; Again above-mentioned mixed two kinds of raw materials are dried processing respectively in drying plant, bake out temperature is 100～140 ℃, and the time is 2～4h; Adopt pressing methods to make the ball core respectively on ball press two kinds of raw materials after the above-mentioned oven dry processing, the control of ball core size determines that by screening the diameter that obtains two kinds of ball cores is 15～40mm; Get the required powder of shell by said ratio and carry out thorough mixing in blender, calcium oxide, magnesian activity 〉=200ml, mixing time are 1～3h.Two kinds of ball cores that made are carried out compound system ball with above-mentioned shell material respectively by scrolling method respectively on balling disc, control definite by screening to the spheroid size, two kinds of composite spheres that make are of a size of 20～80mm, at last with two kinds of composite spheres respectively 90～160 ℃ of oven dry, drying time 10～15h, be cooled to room temperature they are packed 10kg～30kg/ bag respectively, and in 20 days, use.
Embodiment 7
The preparation fine oxide dispersion steel: behind steel liquid deoxidation, begin the forward direction molten steel in the VD refining and spray into pulvis, delivering gas is CO
2, carry air pressure to be controlled at 0.01～2.0MPa, feed quantity is at 0.3～1.5kg/t, and the pulvis transfer rate is taken out of at 0.01～3.5kg/s, and ladle is transported to the refining of RH station; When sampling analysis molten steel oxygen level 0.0001～0.008% the time; the composite sphere that the ball core is mainly useful oxide compound, swelling agent adds molten steel; adding the implantation site is the downtake place of tremie pipe offside, and spheroid is taken out of cast after adding back circulation 1～5min immediately, and continuous casting adopts the whole process protection cast.
The preparation of described pulvis is at first got CaO65kg, Al by formulation ratio
2O
315kg, SiO
28kg, CaF
212kg, the method for preparing low melting point fritting ground-slag is with embodiment 1; Getting particle diameter is that low melting point fritting ground-slag 1kg, lime carbonate 1kg, the magnesium oxide 98kg that 1nm～3.5mm prepares puts into vertical mixing batch mixing 2～8h; Dry processing again on drying plant, bake out temperature is 80～200 ℃, and the time is that 8～20h is the finished product pulvis.Be cooled to room temperature and pack in the ultra-thin high-strength polyethylene plastics bag, moisture sealed packing 500kg/ bag, packing will be guaranteed good seal, prevents humidity, and uses in 20 days.
The preparation of described composite sphere, with embodiment 1, no longer chela is stated.
For the effect that adopts the present invention to prepare the fine oxide dispersion steel processing method better is described, carried out following simultaneous test:
Example:
The kind carbon content of producing is 0.0030%.The converter tapping carbon content is controlled at 0.03～0.04%.
Regulate the position of RH downtake and tremie pipe, make it to be in the heteropleural of tremie pipe.After molten steel is transported to the RH station, the thermometric sampling, smelting process molten steel actual temperature is higher than 5～10 ℃ of the temperature of needs, regulate composition, after alloying finishes, and when vacuum degree in vacuum chamber during at 80～350Pa, drop into the composite sphere that contains second kind of ball core the embodiment 6 from the alloy feed bin, add back circulation 1～15min, feed quantity is at 0.3～1.5kg/t, and feeding speed is at 0.01～2.0kg/s.When sampling analysis molten steel oxygen level 0.0001～0.008% the time; the composite sphere that contains first kind of ball core among the embodiment 6 is added molten steel in the RH refining process; adding the implantation site is the downtake place of tremie pipe offside; add-on is 0.5～3.5kg/t; the single add-on is at 50～130kg, and twice adding is at interval at 0.1～5min, and 1～10min at least circulates after spheroid adds; take out of, go up the machine casting, continuous casting adopts the whole process protection cast.
Comparative example:
The kind carbon content of producing is 0.0030%, and the converter tapping carbon content is controlled at 0.03～0.04%.After 100 tons of molten steel are transported to the RH station, vacuumize, thermometric sampling, regulate composition, circulate, take out of, go up the machine casting only, continuous casting adopts the whole process protection cast.
Table 1
| The big or small d of oxide inclusion i， μm | The oxide inclusion number density, N v×10 -5(mm -3) | |
| Example | 0.1～1 | 6.34 |
| Comparative example | 3～15 | 0.88 |
Claims (19)
1, the processing method of preparation fine oxide dispersion steel is characterized in that may further comprise the steps:
(i) removal of deoxidation products: behind steel liquid deoxidation,, feed pulvis, cored-wire, compound ball ball or composite sphere to molten steel at LF, RH, VD or CAS-OB by dusting, line feeding, penetrating the directly method of feeding of ball or spheroid;
The (ii) generation of disperse oxide: when the molten steel oxygen level 0.0001%～0.008% the time, the composite sphere that the ball core is mainly useful oxide compound, swelling agent adds molten steel in the RH refining process.
2, processing method according to claim 1 is characterized in that step I is described to feed described pulvis, cored-wire, compound ball ball or composite sphere at LF, RH, VD or CAS-OB station to molten steel:
(1) pulvis: finish to spray into molten steel before back or VD refining begin in LF, RH, VD or CAS-OB refining, delivering gas is Ar, CO
2In the mixed gas of any one or the two, carry air pressure to be controlled at 0.01～2.0MPa, the pulvis feed quantity is at 0.3～1.5kg/t, the pulvis transfer rate is at 0.01～3.5kg/s.
(2) cored-wire: finish the back feeding in LF, RH, VD or CAS-OB refining later stage alloying, the line feeding process stops Argon and stirs, wire-feeding velocity is at 180～350m/min, feed quantity is at 50～800m/t, static 0.5～10min after the line feeding, carry out Argon again and gently handle, the flow of argon gas is 50～280Nl/min, and weak argon blowing time is 0.5～5min.
(3) compound ball ball: penetrate ball at LF, RH or CAS-OB refining later stage, adopt Ar, CO
2In the mixed gas of any one or the two as carrier, air pressure is controlled at 0.1～1.0MPa.The amount of injecting is 0.5～5kg/t, and feeding speed is at 0.1～3.0kg/s.
(4) composite sphere: add in the RH refining treatment later stage, the vacuum tightness of RH is at 66.7～500Pa.Adding the implantation site is the downtake place of tremie pipe offside, adds back circulation 1～15min, and feed quantity is at 0.3～1.5kg/t, and feeding speed is at 0.01～2.0kg/s.
3, processing method according to claim 1, the add-on that it is characterized in that the described composite sphere of step I i is 0.5～3.5kg/t, and the single add-on is at 50～130kg, and adding speed is 0.1～1.5kg/s.
4, processing method according to claim 1 is characterized in that described pulvis is prepared from by following raw materials by weight:
Low melting point pre-melted slag pulvis 1～70%
The mixture 1～60% of lime carbonate, magnesiumcarbonate or lime carbonate and magnesiumcarbonate
Calcium oxide or magnesium oxide or calcium oxide and magnesian mixture 10～98%
Calcium Fluoride (Fluorspan) 0～40%
Binding agent 0～20%
5, processing method according to claim 1 is characterized in that described pulvis is prepared from by following raw materials by weight:
Low melting point pre-melted slag pulvis 10～50%
The mixture 10～45% of lime carbonate, magnesiumcarbonate or lime carbonate and magnesiumcarbonate
Calcium oxide or magnesium oxide or calcium oxide and magnesian mixture 30～70%
Calcium Fluoride (Fluorspan) 5～30%
Binding agent 5～15%
6, processing method according to claim 1 is characterized in that described cored-wire is a core with above-mentioned powder, is that crust is prepared from the thick mild-carbon steel strip of 2～5mm.
7, processing method according to claim 1 is characterized in that described composite sphere is to be made of ball core and shell, and described shell mainly is made of calcium oxide or magnesian one or both mixture.
8, processing method according to claim 7 is characterized in that described ball core is prepared from by following raw materials by weight:
Useful oxide compound 0.1～99%
Swelling agent 1～70%
Binding agent 0～30%
9, processing method according to claim 7 is characterized in that described ball core is prepared from by following raw materials by weight:
Useful oxide compound 30～80%
Swelling agent 8～55%
Binding agent 5～15%
10, processing method according to claim 7 is characterized in that described ball core is prepared from by following raw materials by weight:
Low melting point pre-melted slag pulvis 1～70%
Swelling agent 1～60%
Calcium Fluoride (Fluorspan) 0～40%
Binding agent 0～20%
11, processing method according to claim 7 is characterized in that described ball core is prepared from by following raw materials by weight:
Low melting point pre-melted slag pulvis 10～50%
Swelling agent 10～45%
Calcium Fluoride (Fluorspan) 5～30%
Binding agent 5～15%
12, processing method according to claim 1 is characterized in that the ball core of the described compound ball ball of step I, composite sphere is mainly low melting point pre-melted slag pulvis, swelling agent.
13, processing method according to claim 7 is characterized in that described shell also comprises 0～20% binding agent.
14, according to Claim 8 or 9 described processing methodes, it is characterized in that described useful oxide compound is CaO, Ti
2O
3, ZrO
2With in the rare earth oxide any one.
15, processing method according to claim 14 is characterized in that described rare earth oxide is to contain in Ce, Nd, La, Gd, the Sm oxide compound any one.
16, according to Claim 8,9,10,11 or 12 described processing methodes, it is characterized in that described swelling agent is made of the mixture of lime carbonate, magnesiumcarbonate or lime carbonate and magnesiumcarbonate.
17, according to claim 4,5,10,11 or 12 described processing methodes, it is characterized in that described low melting point pre-melted slag pulvis by following raw materials by weight through being prepared from: CaO 10～70%, Al
2O
315～50%, SiO
20～10%, MgO 0～10%, CaF
20～30%, its fusing point is at 1100 ℃～1550 ℃.
18,, it is characterized in that described binding agent is any one or a two or more mixture in clay, Portland cement, wilkinite, the water glass according to claim 4,5,8,9,10,11 or 13 described processing methodes.
19, according to claim 4,5,8,9,10 or 11 described processing methodes, the granularity that it is characterized in that described raw material is at 1nm～3.5mm, wherein calcium oxide, magnesian activity 〉=200ml.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102766731A (en) * | 2012-07-03 | 2012-11-07 | 南京钢铁股份有限公司 | Vacuum refining process |
| CN106244761A (en) * | 2016-07-28 | 2016-12-21 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of preparation method of high-cleanness, high IF steel |
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| CN1056415C (en) * | 1998-04-07 | 2000-09-13 | 幸超 | Aluminium-contained premelting slag and preparation method therefor, and molten steel desulfurizer and purifier containing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102766731A (en) * | 2012-07-03 | 2012-11-07 | 南京钢铁股份有限公司 | Vacuum refining process |
| CN106244761A (en) * | 2016-07-28 | 2016-12-21 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of preparation method of high-cleanness, high IF steel |
| CN106244762A (en) * | 2016-07-28 | 2016-12-21 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of control method of IF steel clamp foreign material |
| CN106244762B (en) * | 2016-07-28 | 2018-08-14 | 成都先进金属材料产业技术研究院有限公司 | A kind of control method of IF steel clamps sundries |
| CN106244761B (en) * | 2016-07-28 | 2018-11-16 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of preparation method of high-cleanness, high IF steel |
| CN108034834A (en) * | 2017-11-14 | 2018-05-15 | 邢台钢铁有限责任公司 | A kind of production method of small lot electroslag remelting pre-melted slag |
| CN108034834B (en) * | 2017-11-14 | 2019-10-18 | 邢台钢铁有限责任公司 | A kind of production method of small lot electroslag remelting pre-melted slag |
| CN112899436A (en) * | 2021-03-29 | 2021-06-04 | 安徽工业大学 | Method for adding oxide particles into molten steel |
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| CN100552052C (en) | 2009-10-21 |
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