CN102943148A - Method for producing high-purity stainless steel - Google Patents
Method for producing high-purity stainless steel Download PDFInfo
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- CN102943148A CN102943148A CN2012105076741A CN201210507674A CN102943148A CN 102943148 A CN102943148 A CN 102943148A CN 2012105076741 A CN2012105076741 A CN 2012105076741A CN 201210507674 A CN201210507674 A CN 201210507674A CN 102943148 A CN102943148 A CN 102943148A
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Abstract
The invention relates to a method for producing a high-purity stainless steel. The method comprises the following steps: molten raw materials are put in an argon oxygen decarburization (AOD) refining furnace to be decarburized, reduced and desulfurized, so that molten steel is obtained; then the molten steel is delivered to a steel ladle; and the molten steel is continuously cast, wherein the treatment of the AOD refining furnace comprises the following steps: after the oxygen blowing decarburization is finished, ferrosilicon is put, meanwhile, slagging and desulfurizing are carried out, the desulfurizing is finished until the S content in the furnace is smaller than 0.01wt%, steel is tapped into the steel ladle from the AOD refining furnace for the first time, after the steel ladle is slagged off, the molten steel is added into the AOD refining furnace again to be slagged again, oxygen is blown, the slag basicity is controlled within the range of 1.4-1.8, argon is then blown, the molten steel is stirred until the S content in the furnace is smaller than 0.01%, and the steel is tapped from the AOD refining furnace again so as to obtain the molten steel. The method adopts the AOD refining furnace, a double-slagging method is adopted, and hard slag inclusions are prevented from being produced, and thus, the high-purity stainless steel is produced.
Description
Technical field
The present invention relates to a kind of high pure stainless preparation method, belong to the stainless steel smelting field.
Background technology
Learn that by the prior art document shown in Fig. 1 a and Fig. 1 b of CN1524968A, when having rigid inclusion in the stainless steel, illustrated defective can appear in the surface of preparation-obtained cold-rolled steel coils.This is because these inclusiones do not have deformability at low temperatures, can cause surface imperfection or crackle in cold rolling calendering.Fig. 2 of CN1524968A is the graphic representation of the relation between spinel rate of formation and the surface imperfection index in the cold-rolled steel coils.Wherein, spinel rate of formation (%)=spinels inclusion number/all the inclusion number of observing * 100, the linear flaws number that surface imperfection index=inclusion causes/1km cold-rolled steel coils.As shown in Figure 2, the surface imperfection of cold-rolled steel coils and the spinel rate of formation in the continuously cast bloom have close relationship, when the spinel rate of formation is lower than 40% in the continuously cast bloom, just can produce the good cold-rolled steel coils of the quality of surface imperfection index below 1.Therefore, go for surface quality good high pure stainless-steel cold-rolling coil of strip or steel plate, the rigid spinel (MgOAl in the control continuously cast bloom
2O
3) content of inclusion is most important.
In stainless steel refining process, remove the technique that above-mentioned rigid inclusion or inclusion modifying process reveal the inclusion eutectic and generally in argon oxygen decarburization (AOD) refining furnace, implement.During the AOD refining at first oxygen blast carbon is taken off target content, drop into again reductive agent ferrosilicon and lime, slag making materialses such as fluorite, and be blown into the stirring of inert gas such as argon gas.By above-mentioned technique, can realize decarburization, reduction, desulfurization such as goes to be mingled with at the function.
Usually, when the AOD refining for fear of MgOAl occurring
2O
3Or Al
2O
3Etc. rigid inclusion, usually adopt the silicomanganese complex deoxidization.But still a part of MgOAl can appear in the refining process
2O
3Or Al
2O
3Etc. rigid inclusion, its reason is as follows: because after the AOD refining end, the mode that adopts the slag steel reinforced concrete to go out, in tapping process, slag can be rolled in the molten steel, causes a large amount of slags to drip and is suspended in the molten steel, can not come-up get rid of from molten steel if wherein less slag drips before molten steel enters continuous cast mold, will remain in the continuously cast bloom, become inclusion.Such as Fig. 3 (Formation Mechanism of Spinel-Type Inclusions in High-Alloyed Stainless Steel Melts, J.H.Park:Metall.Trans.B, 38B (2007), 657.) shown in, these be suspended in the molten steel inclusion can along with the reduction of temperature from the AOD refining furnace tap the casting process with molten steel in the Al reaction, thereby composition changes, and finally becomes spinel (MgOAl
2O
3) inclusion.Accordingly, the degree that composition of inclusions changes, relevant with the Al content in the molten steel, the Al content in the molten steel will become spinel (MgOAl in the time of high
2O
3) inclusion.Even adopt the silicomanganese complex deoxidization, still understand some Al and be brought into the molten steel from raw material or alternate manner, when Al concentration in the molten steel MgOAl will occur after surpassing a certain value
2O
3Or Al
2O
3Etc. rigid inclusion.(the FormationMechanism of Spinel Type Inclusion in 304stainless steel Deoxidized with FerrosiliconAlloys such as Todoroki, H.Todoroki, K.Mizuno, M.Noda and T.Tohge:84th Steelmaking.Conf.Proc., Baltimore, MD, ISS, (2001), 331.) by experiment the chamber studies have shown that the relation of Al content between occurring with the spinel inclusion thing, and provided phase stability diagram as shown in Figure 4.As can be seen from Figure 4, even have a small amount of Al (＜0.01%) in the molten steel, inclusion also can become spinel (MgOAl from silicate
2O
3).
In sum, whether spinel (MgO.Al appears
2O
3) inclusion has close relationship with the Al content in the molten steel.Al content in the molten steel except the Al content that is subjected to bring in the raw material have outside the Pass also with the basicity (CaO/SiO of slag
2), the kind of anti-material, %Al in the slag
2O
3Content is relevant.This is owing to there is the slag steel balance shown in the following reversible chemical reaction formula: 2Al in the AOD refining
2O
3+ 3Si=3SiO
2+ 4Al, Al in this formula
2O
3, SiO
2Aluminium sesquioxide is with silicon-dioxide in the expression slag, and Si, Al represent silicon and the aluminium in the molten steel.From reaction formula, can find out, increase the Al in the slag
2O
3Or the SiO in the reduction slag
2Namely improve basicity (CaO/SiO
2), reaction is moved right, cause the aluminium in the molten steel to increase.Therefore, the aluminium content that reduces in the molten steel can solve from three aspects:: 1, reduce the raw material or the source of the Al in the anti-material; 2, reduce basicity of slag (CaO/SiO
2); 3. Al in the minimizing slag
2O
3Content.
CN1524968A discloses a kind of method of refining of high-purity stainless steel, in the method, and in order to prevent rigid inclusion MgOAl
2O
3Appearance, refining furnace reducing slag basicity (CaO/SiO
2) be controlled between 1.5 to 1.8, and %MgO+%Al in the control reducing slag
2O
3＜13%.It is offscale that sulphur is protected in the finished product in simultaneously pre-desulfurization before AOD packs into, the lower level of sulphur of guaranteeing to pack in the refining furnace.
Prior art all is with low basicity (basicity (CaO/SiO basically
2)＜1.9) be feature, and control %MgO and %Al in the slag
2O
3Content.But, low basicity (CaO/SiO
2) can cause the decline of refining furnace sweetening power, low basicity (CaO/SiO when the S content of bringing in the raw material is higher
2) can cause the sulphur in the product to transfinite.At low basicity (CaO/SiO
2) situation under, be no more than set upper limit in order to make the sulphur in the product, can only reduce sulphur in the product by reducing sulphur content in the raw material.Since under the low basicity condition between the slag steel partition ratio of sulphur probably be 30, the concentration of this sulphur that just requires to pack in the AOD refining furnace is less than 0.015wt%.This method can cause the low price raw material usage quantity to reduce, and expense of raw materials rises, and the source of sulphur is many in the raw material, and control is got up very unstable, and the sulphur height that often occurs in the raw material causes the sulphur in the product to transfinite.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of high pure stainless preparation method.The object of the present invention is to provide a kind of high pure stainless preparation method.This preparation method adopts the AOD refining furnace, by control sulfur removal technology and slagging method, prevents from occurring dystectic rigid inclusion in the product, thereby prepares the high pure stainless steel that does not have surface imperfection.
The present invention also aims to provide a kind of high pure stainless steel, it obtains by above-mentioned preparation method is prepared.
For reaching above-mentioned purpose, the invention provides a kind of high pure stainless preparation method, this preparation method may further comprise the steps: the raw material after will melting places the AOD refining furnace to process, and obtains molten steel; Then tap to from the AOD refining furnace and build ladle; Carry out again continuous casting, obtain continuously cast bloom;
Wherein, placing the AOD refining furnace to process the raw material after the fusing may further comprise the steps:
After oxygen decarburization finishes in the a.AOD refining furnace, drop into chromic oxide in the reduction by ferrosilicon slag, simultaneously slag making desulfurization, desulfurization is to the stove during S content＜0.01 % by weight, from the AOD refining furnace, tap to ladle for the first time, thoroughly skim in ladle, the molten steel after then will skimming is blended in the AOD refining furnace again;
B. after molten steel is blended into the AOD refining furnace again, be blown into oxygen, the silicon in the molten steel of oxidation is to produce SiO
2, and control basicity of slag (CaO/SiO
2) in the scope of 1.4-1.8; After oxygen is blown into end, is blown into argon gas and stirs, S content＜0.01 % by weight to the stove, for the second time tapping from the AOD refining furnace obtains molten steel.
In above-mentioned preparation method, preferably, the method is further comprising the steps of: with described continuously cast bloom carry out successively hot rolling and cold rolling after, obtain the pure stainless steel of described height.
In above-mentioned preparation method, preferably, after the oxygen decarburization of step a finishes, when dropping in the reduction by ferrosilicon slag chromic oxide, add lime and fluorite slag making; The ferrosilicon input amount is ton steel 15kg-30kg; The lime input amount is ton steel 40kg-100kg, makes basicity of slag (CaO/SiO
2) be controlled at more than 1.8; The fluorite input amount is the 15%-25% of lime input amount.Wherein, the effect of lime is to regulate basicity, and the effect of fluorite is to make slag have good flowability.
In above-mentioned preparation method, preferably, in step a, blowing argon gas and stirring are carried out in the slag making desulfurization.
In above-mentioned preparation method, preferably, in step a, from the AOD refining furnace, tap to ladle for the first time, after in ladle, skimming, residual thickness of slag layer＜50mm.
In above-mentioned preparation method, preferably, in step b, be blown into amount of oxygen and be ton steel 4Nm
3-6Nm
3When being blown into oxygen, drop into lime and fluorite, the lime input amount is ton steel 15Kg-18Kg, the fluorite input amount is the 15%-25% of lime input amount, makes ton slag amount greater than 30kg.
In above-mentioned preparation method, preferably, in step b, the time of blowing argon gas, the reaction of slag steel reached balance to make slag fully melt also greater than 5min.
In above-mentioned preparation method's step b, be blown into oxygen and make the silicon in the molten steel fully be oxidized to SiO
2After, can stop oxygen blast, those skilled in the art can judge when finish oxygen blast according to description of the invention.
In above-mentioned preparation method, preferably, described ladle is the rhombspar ladle.By using the rhombspar ladle, can reduce the Al in the slag
2O
3Content is to prevent the appearance of spinel inclusion thing.
In above-mentioned preparation method, preferably, in weight percentage, the ferrosilicon that uses is the ferrosilicon of aluminium content＜0.1%.By using the ferrosilicon of low-aluminum-content, can reduce the Al that brings in the raw material, thereby avoid the appearance of spinel inclusion thing.
In above-mentioned preparation method, preferably, the raw material of all uses all is the raw material of conventional specification, and sulphur content is not done special restriction.
In above-mentioned preparation method, preferably, with described continuously cast bloom carry out successively hot rolling and cold rolling after, obtain cold-rolled steel coils.The thickness of described cold-rolled steel coils is less than 0.3mm.
In preparation method of the present invention, the melting operation that is molten into this area routine of raw material can be carried out in electric furnace; Therefore continuous casting, hot rolling and the cold rolling common process that is this area, Ao Shu no longer.
The invention provides a kind of high pure stainless steel, it obtains by above-mentioned preparation method is prepared.Rigid inclusion MgOAl in the pure stainless steel of this height
2O
3Incidence be 0%.
The pure stainless preparation method of height of the present invention adopts the AOD refining furnace, by double slag process, under the AOD refining furnace is packed the higher situation of sulphur into, preferably desulfurization, can suppress again the generation of rigid inclusion, thereby prepare more economically the high pure stainless steel that does not have surface imperfection.
Description of drawings
Fig. 1 a represents owing to rigid MgOAl in the STS steel
2O
3The linear flaws on the cold-rolled steel coils surface that inclusion causes;
Fig. 1 b represents owing to rigid MgOAl in the STS steel
2O
3The processing crackle on the cold-rolled steel coils surface that inclusion causes;
Fig. 2 represents the graphic representation of the relation between the spinel rate of formation and surface imperfection index in the cold-rolled steel coils;
Fig. 3 represents that the composition that is suspended in the inclusion in the molten steel from the AOD refining furnace is tapped casting process changes;
Fig. 4 represents the phase stability diagram of Al, Mg concentration in the molten steel;
Fig. 5 represents the distribution of Inclusion During Slab Casting composition in phasor that embodiment 1 makes.
Embodiment
According to the pure stainless chemical ingredients of height to be prepared (be shown in Table 1, embodiment 1 and 2 preparations be the STS304 steel), with waste stainless steel, high carbon ferro-chrome, the raw materials such as the nickel pig iron are packed into and are melted in 140 tons of electric furnaces;
Main raw material after will melting in electric furnace places 150 tons of AOD refining furnaces to carry out Decarburising and refining and processes: after decarburization finished, the ton steel dropped into the 25kg ferrosilicon, 80kg lime, and the 16kg fluorite, blowing argon gas stirs and carries out reduction and desulfurization simultaneously, and the control basicity of slag is 2.2; Behind S in the steel fusion＜0.01%, the mode of mixing out with the slag ladle of tapping; In the ladle utilization slag machine is skimmed thoroughly, the rear residual slag thickness of skimming is less than 30mm;
Molten steel is blended into AOD and ton steel oxygen blast 4Nm again after having taken off slag
3, dropping into simultaneously ton steel 15Kg lime, the 3kg fluorite is made new slag, and the control basicity of slag is 1.5, and the quantity of slag is ton steel 30Kg; After oxygen blast finished, Argon stirred in 8 minutes simultaneously, made the reaction of slag steel reach sufficient balance; After Argon finished, the AOD refining furnace was tapped for the second time, obtained molten steel, then built ladle, again through continuous casting, obtained continuous casting steel billet; With described continuous casting steel billet carry out hot rolling and cold rolling after, make thickness 0.3mm, the coil of strip of width 1200mm.
In aforesaid method, employed ladle is the rhombspar ladle.Ferrosilicon in the raw material that adopts is the ferrosilicon of aluminium content＜0.1% (weight percentage).
Comparative Examples 1 and 2
Comparative Examples 1 and 2 provides respectively a kind of stainless preparation method who adopts existing technique, and those skilled in the art can learn its concrete steps, therefore Ao Shu no longer.
The high pure stainless composition (wt%) of table 1 embodiment and Comparative Examples
| C | Si | Mn | Cr | Ni | S | N |
| 0.035 | 0.5 | 1.1 | 18.2 | 8.1 | ＜0.01 | 0.035 |
Table 2
In addition, Fig. 5 is the distribution of Inclusion During Slab Casting composition in phasor that embodiment 1 makes.As can be seen from Figure 5, the inclusion in the continuous casting steel billet that embodiment 1 makes all is distributed in the low melting range (fusing point＜1300 ℃), does not have dystectic inclusion, does not namely have the rigid inclusiones such as spinel.
In sum, the pure stainless preparation method of height provided by the invention, by control sulfur removal technology and slagging method, can prevent from occurring in the continuously cast bloom dystectic rigid inclusion, improve the ductility of inclusion described in the subsequent technique, prevent surface imperfection and the crackle of the finished product, and improved simultaneously the economy of producing.
Claims (10)
1. one kind high pure stainless preparation method, this preparation method may further comprise the steps: the raw material after will melting places the AOD refining furnace to process, and obtains molten steel; Then tap to from the AOD refining furnace and build ladle; Carry out again continuous casting, obtain continuously cast bloom; Wherein, placing the AOD refining furnace to process the raw material after the fusing may further comprise the steps:
After oxygen decarburization finishes in the a.AOD refining furnace, drop into chromic oxide in the reduction by ferrosilicon slag, simultaneously slag making desulfurization, desulfurization is to the stove during S content＜0.01 % by weight, from the AOD refining furnace, tap to ladle for the first time, skim in ladle, the molten steel after then will skimming is blended in the AOD refining furnace again;
B. after molten steel is blended into the AOD refining furnace again, be blown into oxygen, the silicon in the molten steel of oxidation is with generation SiO2, and the control basicity of slag is in the scope of 1.4-1.8; After oxygen is blown into end, is blown into argon gas and stirs, S content＜0.01 % by weight to the stove, for the second time tapping from the AOD refining furnace obtains molten steel.
2. preparation method as claimed in claim 1, the method also comprise with described continuously cast bloom carry out successively hot rolling and cold rolling after, obtain the pure stainless steel of described height.
3. preparation method as claimed in claim 1 or 2 wherein, after the oxygen decarburization of step a finishes, when dropping in the reduction by ferrosilicon slag chromic oxide, adds lime and fluorite slag making; The ferrosilicon input amount is ton steel 15kg-30kg; The lime input amount is ton steel 40kg-100kg, and basicity of slag is controlled at more than 1.8; The fluorite input amount is the 15%-25% of lime input amount.
4. such as each described preparation method of claim 1-3, wherein, in step a, from the AOD refining furnace, tap to ladle for the first time, after in ladle, skimming, residual thickness of slag layer＜50mm.
5. such as each described preparation method of claim 1-4, wherein, in step b, be blown into amount of oxygen and be ton steel 4Nm
3-6Nm
3When being blown into oxygen, drop into lime and fluorite, the lime input amount is ton steel 15Kg-18Kg, the fluorite input amount is the 15%-25% of lime input amount, makes ton slag amount greater than 30kg.
6. such as each described preparation method of claim 1-5, wherein, in step b, the time of blowing argon gas is greater than 5min.
7. such as each described preparation method of claim 1-6, wherein, described ladle is the rhombspar ladle.
8. such as each described preparation method of claim 1-7, wherein, in weight percentage, the ferrosilicon that uses is the ferrosilicon of aluminium content＜0.1%.
9. such as each described preparation method of claim 1-8, wherein, with described continuously cast bloom carry out successively hot rolling and cold rolling after, obtain cold-rolled steel coils.
10. one kind high pure stainless steel, it is prepared the obtaining of the pure stainless preparation method of each described height of claim 1-9.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104357617A (en) * | 2014-10-31 | 2015-02-18 | 安徽应流集团霍山铸造有限公司 | Method for secondarily refining super-clean molten metal in AOD furnace |
| CN105567907A (en) * | 2016-01-06 | 2016-05-11 | 山西太钢不锈钢股份有限公司 | Method for controlling plastic inclusions of austenitic stainless steel |
| CN106011380A (en) * | 2016-07-08 | 2016-10-12 | 邢台钢铁有限责任公司 | Method for conducting molten iron desulphurization through AOD |
| CN110014248A (en) * | 2019-05-15 | 2019-07-16 | 丹阳市华龙特钢有限公司 | A kind of preparation method of Ni-based high-temperature-resistant and anti-corrosion welding wire |
| CN110016590A (en) * | 2019-05-15 | 2019-07-16 | 丹阳市华龙特钢有限公司 | A kind of Superalloy In Aerospace Technology material |
| CN110016625A (en) * | 2019-05-15 | 2019-07-16 | 丹阳市华龙特钢有限公司 | High-purity anti-corrosive alloy material |
| CN110106378A (en) * | 2019-05-15 | 2019-08-09 | 丹阳市华龙特钢有限公司 | A kind of preparation method of nickel base superalloy |
| CN110819896A (en) * | 2019-11-13 | 2020-02-21 | 甘肃酒钢集团宏兴钢铁股份有限公司 | Smelting method of ultrathin austenitic stainless steel strip for precision calendering |
| CN112342454A (en) * | 2020-10-16 | 2021-02-09 | 浦项(张家港)不锈钢股份有限公司 | 316L stainless steel and preparation method thereof |
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| CN104357617A (en) * | 2014-10-31 | 2015-02-18 | 安徽应流集团霍山铸造有限公司 | Method for secondarily refining super-clean molten metal in AOD furnace |
| CN105567907A (en) * | 2016-01-06 | 2016-05-11 | 山西太钢不锈钢股份有限公司 | Method for controlling plastic inclusions of austenitic stainless steel |
| CN106011380A (en) * | 2016-07-08 | 2016-10-12 | 邢台钢铁有限责任公司 | Method for conducting molten iron desulphurization through AOD |
| CN110106378A (en) * | 2019-05-15 | 2019-08-09 | 丹阳市华龙特钢有限公司 | A kind of preparation method of nickel base superalloy |
| CN110016590A (en) * | 2019-05-15 | 2019-07-16 | 丹阳市华龙特钢有限公司 | A kind of Superalloy In Aerospace Technology material |
| CN110016625A (en) * | 2019-05-15 | 2019-07-16 | 丹阳市华龙特钢有限公司 | High-purity anti-corrosive alloy material |
| CN110014248A (en) * | 2019-05-15 | 2019-07-16 | 丹阳市华龙特钢有限公司 | A kind of preparation method of Ni-based high-temperature-resistant and anti-corrosion welding wire |
| CN110016590B (en) * | 2019-05-15 | 2021-04-06 | 丹阳市华龙特钢有限公司 | High-temperature alloy material for aerospace |
| CN110016625B (en) * | 2019-05-15 | 2021-08-03 | 丹阳市华龙特钢有限公司 | High-purity corrosion-resistant alloy material |
| CN110819896A (en) * | 2019-11-13 | 2020-02-21 | 甘肃酒钢集团宏兴钢铁股份有限公司 | Smelting method of ultrathin austenitic stainless steel strip for precision calendering |
| CN112342454A (en) * | 2020-10-16 | 2021-02-09 | 浦项(张家港)不锈钢股份有限公司 | 316L stainless steel and preparation method thereof |
| CN112342454B (en) * | 2020-10-16 | 2022-03-04 | 浦项(张家港)不锈钢股份有限公司 | 316L stainless steel and preparation method thereof |
| CN114318176A (en) * | 2021-12-24 | 2022-04-12 | 浦项(张家港)不锈钢股份有限公司 | Manufacturing method of soft 304L stainless steel, stainless steel and application |
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