CN101643822B - Ultrahigh basicity low aluminum fluorine-free refining slag and preparation method and use method thereof - Google Patents
Ultrahigh basicity low aluminum fluorine-free refining slag and preparation method and use method thereof Download PDFInfo
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- CN101643822B CN101643822B CN2009101845964A CN200910184596A CN101643822B CN 101643822 B CN101643822 B CN 101643822B CN 2009101845964 A CN2009101845964 A CN 2009101845964A CN 200910184596 A CN200910184596 A CN 200910184596A CN 101643822 B CN101643822 B CN 101643822B
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Abstract
The invention relates to an ultrahigh basicity low aluminum fluorine-free refining slag and a preparation method and a use method thereof, belonging to the technical field of steelmaking and refining. The refining slag comprises the following chemical compositions by weight percent: 85-95% of CaO, 2-10% of B2O3, 2-10% of MgO, 1-10% of Al2O3 and less than 5% impurities, wherein the content of harmful impurities such as sulfur, phosphorus and the like is as low as possible. The refining slag is prepared by using industrial reagents, namely active lime, boron anhydride, magnesia and aluminium ash to prepare, premelting at 1350-1450 DEG C, cooling, crushing to 2-10mm and performing moisture proof packaging. The slag series can be used for the refining and slag forming of LF, RH and CAS and the refining slag is added in steel ladle in the process of argon blowing after the molten steel preliminary deoxidation and the reduction treatment of the residue of steel ladle. The refining slag of the invention has strong desulphurizing and dephosphorizing abilities and no pollution, the slag inclusion generated through absorption and deoxidation has higher ability, the deoxidation effect of steel is improved, the spreadability is good, the suction and oxidation of the molten steel are reduced, the refining devices do not adhere to slag, the preparation process is simple, and the product is easy to store and use.
Description
Technical field
The present invention relates to a kind of fluorine-free pro-molten shaped steel bag refining slag and preparation method thereof and using method, belong to steel-making external refining field, be applicable to slag making refining process in ladle with ultra-high basicity.
Background technology
Along with socioeconomic development, the user has proposed more and more higher requirement to the quality of steel, and external refining plays a part very important in whole Steel Production Flow Chart as the important production process in the modern steelmaking process.In many refinery practices, the synthetic slag refining has desulfurization, dephosphorization, deoxidation and receives functions such as steel inclusion, is widely used and develops.
At present, the steel-making furnace steel refining slag mainly comprises following basis series: CaO-CaF
2Slag system; CaO-Al
2O
3Slag system; CaO-Al
2O
3-CaF
2Slag system.In these three basic slag systems, the constituent element that really plays desulfurization, phosphorus refining effect mainly is CaO, and CaO is cheap and have very strong desulfuration phosphorus ability, but because the fusing point of CaO is very high, needs to add the fusing assistant CaF of higher amount
2, i.e. CaO-CaF
2Slag system is because CaF
2Temperature instability, cause serious fluoride pollution, and single use CaF
2, the poor stability of slag is unfavorable for operating direct motion, and this has been the common recognition on metallurgical boundary.Recognizing CaF
2Do after the harm of flux, CaO-Al is brought into use in the external refining slag making
2O
3Slag system has been eliminated fluoride pollution, but because Al
2O
3Fluxing action a little less than, Al in this slag system
2O
3Occupy big component, watered down the effect of CaO as desulfurization, phosphorus constituent element, so that the metallurgical performance of this slag system is relatively poor.At CaO-CaF
2Slag system and CaO-Al
2O
3On the basis of slag system, CaO-Al is adopted in research
2O
3-CaF
2Slag system utilizes Al
2O
3And CaF
2Jointly play the effect of adjusting the slag metallurgical performance, this slag system is the external refining slag system of present extensive use, but along with the raising of the mankind to health, environmental requirement, CaF
2Use amount be subjected to strict restriction, have to increase Al in the slag
2O
3Use amount so that this refining slag system has preferably meltdown property can only be about 60% so that the amount of CaO is the highest in this slag system, this has limited CaO-Al
2O
3-CaF
2The raising of slag system desulfurization, phosphorus ability, also having limited refining slag is Al to the aluminium deoxidation product
2O
3Ability to arrange jobs.Recently, there is the researcher to propose with BaO, Na
2O, Li
2O, SrO etc. replace part or all of CaO, can reduce the use amount of flux, improve simultaneously desulfurization, phosphorus ability, but BaO, Na
2The harm that O brings to the erosion of the pollution of environment, equipment and not second to fluoride pollution, and Li
2O, SrO wish expensive resource very much, so present external refining slag making can only be take the strong CaO of cheapness and desulfurization, phosphorus ability as the basis, but will overcome present employing CaO-CaF
2Slag system, CaO-Al
2O
3Slag system and CaO-Al
2O
3-CaF
2The slag system above shortcomings when guaranteeing the slag meltdown property, make that CaO keeps trying one's best high content in the slag, to improve the ability of refining slag desulfurization, absorb inclusion and deoxidation products, the rephosphorization of control molten steel.
In the prior art of eliminating fluoride pollution, promotionization slag, Chinese invention patent: (application number: 200910029247.5) a kind of ladle refining slag adjusting agent and preparation method and residue adjustment method, propose to adopt quick lime, aluminium ash, magnesia and boric anhydride to press CaO30～60%, Al
2O
330～60%, MgO 2～10%, B
2O
32～10%, preparation pre-melted type slag adjusting agent, it is effective that this invention has residue adjustment, the advantages such as no fluoride pollution, as slag adjusting agent, the use such as cooperation quick lime has preferably refining effect when refining.But this invention is the slag adjusting agent that a kind of refining process uses, can not use as refining slag separately, in other words, not enough or the essential defective that exists when it uses as refining slag mainly is: the content of CaO is lower in (one), this invention, desulfurization, dephosphorizing capacity are limited, even reduce acid deoxidation products such as SiO
2, Al
2O
3Inlet capacity, affect the deep deoxidation effect of molten steel; (2), Al in this invention
2O
3Content higher, although being conducive to slag has reduced refining slag and has absorbed and to hold molten steel aluminium deoxidation product A l
2O
3Ability, be unfavorable for Al in the molten steel
2O
3Discharge, in steel, form field trash, therefore be not suitable for producing Ultra-clean steel.
Chinese invention patent: (application number: 200910029248.X) a kind of ladle refining proposes to adopt quick lime, aluminium ash, magnesia and boric anhydride to press CaO 75～85%, Al with slag adhesion preventing fluorine-free slag modifier and preparation method and using method
2O
310～20%, MgO0～8%, B
2O
35～15%, preparation pre-melted type slag adjusting agent, the major function of this invention prevents the refining equipment dry slag, certainly this invention also has certain effect to improving refining effect, as is conducive to desulfurization, control rephosphorization etc., but same, this invention also is the slag adjusting agent that a kind of refining process uses, weak point when using as refining slag separately also is that the content of two point: CaO of ubi supra is on the low side, affinability deficiency, and Al
2O
3Content is higher to be unfavorable for deoxygenation of liquid steel and to the absorption of field trash, therefore, to be not suitable for producing Ultra-clean steel as refining slag separately.
In sum, be to improve desulfurization, the dephosphorizing capacity of slag, must improve the basicity of slag as far as possible, namely CaO content is high and acid constituent element content is low in the slag, simultaneously, receives the ability of deoxidation products for improving refining slag, needs to reduce Al in the slag
2O
3Amount.In the industrial production, guarantee refining efficiency, this have high alkalinity and low aluminium type refining slag and must be equipped with and compare CaF
2And Al
2O
3More effectively promote the flux that lime melts, just can reach good refining effect.
Therefore, the present invention proposes to adopt ultrahigh basicity low aluminum fluorine-free type refining slag, namely improves the content of CaO in the slag, reduces simultaneously Al in the refining slag
2O
3Amount, thus the concentration of free CaO in the slag improved, improve desulfurization, the phosphorus ability of slag, overcome a large amount of employing Al
2O
3Residue adjustment causes the problem of desulfurization, phosphorus scarce capacity, in addition, a large amount of free CaO is arranged in the slag, has increased refining slag to remaining deoxidation products such as Al in the steel
2O
3, SiO
2Deng the ability to arrange jobs of material, be conducive to improve the deoxygenation of liquid steel effect; Simultaneously for promoting lime to melt, adopt B
2O
3Make flux, do not use CaF
2Thereby, eliminated fluoride pollution and improved slag making speed and smelting stability.
Summary of the invention
The purpose of this invention is to provide a kind of have ultra-high basicity, low aluminium, floride-free type refining slag, overcome present refining slag desulfurization, phosphorus ability low, receive inclusion ability key issues such as easily fluoride pollution, refractory corrosion saturated and that fluorite brings as fusing assistant be serious, better bring into play the metallurgical function of the outer slag making purified of stove, improve the molten steel quality, smelt efficient and refining unit life-span.
The objective of the invention is to realize by following technical proposal:
A kind of superhigh-alkalinity, low aluminium, floride-free type refining slag, it is characterized in that: composition is calculated in mass percent, and CaO 85～95%, B
2O
32～10%, MgO 2～10%, Al
2O
31～10%, the impurity in the refining slag should be less than 5%, and particularly objectionable impurities such as sulphur, phosphorus etc. are more low more good.
In the above-mentioned refining slag, impurity comprises SiO
2, sulphur, phosphorus and compound thereof etc.
The preparation method of the refining slag of above-mentioned composition is characterized in that: by industrial reagent: quickened lime, boric anhydride, magnesia, aluminium ash, and by above-mentioned given composition preparation, the content of impurity is low more good more in the raw material, and its principle of selecting materials is will satisfy SiO after the batching
2, impurity such as sulphur and phosphorus is less than 5%.Should be fully before the raw material weighing dry, through weigh batching, be ground into the following particle of 2mm, fritting is processed behind batch mixing.Coke heating, coal gas heating or electrically heated method are adopted in fritting, and 1350～1400 ℃ of prefusing temperatures after the fusing evenly, are emitted in stove, the liquid slag postcooling of coming out of the stove, and broken processing, size is 2～10mm, keeps dry state down, weather-proof dressing is stand-by.
Adopt the method for refining of this refining slag to be: after the liquid steel pre-deoxidizing Alloying Treatment, enter the refining station, add reductive agent to ladle residue reduction processing, in the Argon process pro-molten refining slag dropped into the molten steel mirror sections, follow-up refinery practice is identical with adopting conventional refining slag at present, and this slag system can be used for refinery practices such as LF refining, RH refining and CAS refining.For the LF refining, because electric arc heated needs making foamed slag, then can will drop into ladle behind this pre-melted slag and the blowing agent mixing, reach then the refining of electrical heating station, also can throw bag at refining process and use.For RH refining and CAS refining, then can behind the ladle argon-blown deslagging, refining slag be dropped into the molten steel mirror sections, dip pipe or cage refining are fallen then, and also can throw bag at refining process and use.The usage quantity of this refining slag is determined according to desulfurization amount, adds 15Kg pre-melted slag, LF refining 30min by molten steel per ton, sulphur content in the molten steel can be reduced to 0.001% by 0.010%, desulfurization degree reaches about 90%, and desire continues dark desulfurization, then suitably increases the quantity of slag or prolongs refining time.
Adopt the refining slag composition of this invention and matching optimization principle that refining requires as follows:
(1), CaO is main desulfurization, dephosphorization constituent element, also is to receive deoxidation products (Al in the steel simultaneously
2O
3, SiO
2And composition) major components, this is the basic reason that this slag system adopts high CaO content, therefore, when the desulfurization task is heavy, the big generation numerous Al of deoxidation amount in big, the ladle of the remaining converter quantity of slag in the ladle
2O
3, SiO
2In the situation Deng deoxidation products, when adopting pre-melted slag of the present invention, but the content capping of CaO or near the high value of the upper limit in the slag; On the contrary, the content of CaO can remove the limit or near the lower value of lower limit in the pre-melted slag;
(2), B
2O
3Be main flux, CaO, MgO content are higher in slag, Al
2O
3When content is low, B
2O
3Content should be got the higher value near the upper limit, so that refining slag has preferably metallurgical effect; Otherwise CaO, MgO content are lower in slag, Al
2O
3When content is higher, B
2O
3The desirable smaller value near lower limit of content, with the saving cost, and the desulphurizing ability of assurance slag.
(3), the main effect of MgO is to reduce the erosion of refining slag to ladle slag line position magnesia carbon refractory, to prolong refractory life.Facts have proved: 4%～6% MgO just can effectively reduce the erosion of ladle liner in the refining slag.Ladle liner corrodes when serious, can increase MgO in the slag (capping 10%), but cause easily liner dry slag and crust.
(4), Al
2O
3Main Function be the viscosity of adjusting slag, to needing to use in a large number the steel grade of aluminium, silicon deoxidation in the ladle, because the deoxidation meeting generates numerous Al
2O
3Deng material, so should reduce Al in the refining slag of preparation
2O
3Content, to increase refining slag to deoxidation products Al
2O
3, SiO
2Ability to arrange jobs; Otherwise, for the lower steel grade of deoxidation amount in the ladle, can suitably improve Al in the refining slag of preparation
2O
3Content, make refining slag that good metallurgical performance be arranged.
(5), impurity should be less than 5% in the slag, SiO wherein
2Can significantly reduce desulfurization, the phosphorus ability of slag, sulphur, phosphorus and compound thereof can directly pollute molten steel, so impurity content is more low more good.
Compared with prior art, major advantage of the present invention is summarized as follows:
(1), this refining slag has ultra-high basicity, have very strong sweetening power, and can control the molten steel rephosphorization;
(2), adopt B
2O
3Make flux, eliminated CaF
2The fluoride pollution that brings as flux;
(3), B
2O
3Fluxing action very strong, the burn-off rate of slag is fast, fusing point is low, the metallurgical performance of slag improves;
(4), residue adjustment component Al in the slag
2O
3The content decrease, namely improved refining slag to Al in the steel
2O
3The ability to arrange jobs of type impurity has also improved free CaO concentration, and desulfurization and control molten steel rephosphorization ability significantly improve;
(5), there is not SiO in the slag
2Or SiO
2Content very low, improved the ability to arrange jobs of refining slag to silicon deoxidation products, silicates inclusion, so the deoxidation effect of steel improves, the inclusion that deoxidation produces in the steel is effectively controlled.
(6), this refining slag form of adopting fritting to process, improved stability and the metallurgical effect of refining slag, improved simultaneously the working environment of operation site.
In sum, compared with prior art, advantage of the present invention is pollution-free, and desulfurization, phosphorus ability are strong, and absorb the inclusion ability raising that steel-deoxidizing produces, the deoxidation effect of steel improves, and has solved the key issue that the outer slag making refining of present steel melting furnace exists, in addition, the spreadability of this refining slag is good, reduce the air-breathing and oxidation of molten steel, refining unit is dry slag not, and preparation technology is simple, be convenient to accumulating and use.
Embodiment
Embodiment
The invention will be further elaborated below in conjunction with embodiment.Embodiment only is used to illustrate the present invention, rather than limits the present invention by any way
(1) preparation of pro-molten refining slag
The raw material that embodiment adopts is as follows, all is weight percentage when below relating to percentage ratio:
The chemical composition of active lime is: 100%＞CaO 〉=90.0,5% 〉=MgO＞0,2.5% 〉=SiO
2＞0, all the other are Al
2O
3Deng trace impurity;
The chemical composition of boric anhydride: 100%＞B
2O
3〉=85.0,5% 〉=CaO＞0,3% 〉=MgO＞0,3% 〉=SiO
2＞0, all the other are trace impurity;
The chemical composition of magnesia: 100%＞MgO 〉=90.0,5% 〉=CaO＞0,3% 〉=Al
2O
3＞0,1% 〉=SiO
2＞0, all the other are trace impurity;
The chemical composition of aluminium ash: 100%＞Al
2O
3〉=90.0,5% 〉=CaO＞0,3% 〉=MgO＞0,1.5% 〉=SiO
2＞0, all the other are trace impurity;
Get above-mentioned raw materials weighing after 100～150 ℃ of lower bakings, press three kinds of batching mode batchings of table 1.Each raw material crushing is become below the 1mm, join new a block in the ladle behind the mechanical mixing, make it 1380 ℃ of fusings down, after the fusing evenly with the coal gas heating, in stove, emit the liquid slag postcooling of coming out of the stove, broken processing, size is 2～10mm, keeps dry state down, and weather-proof dressing is stand-by.(annotate: steel mill could use after need to toasting new block ladle, is energy savings, and present embodiment is exactly fritting slag charge when utilizing ladle baking, and after slag charge melted and empties out, ladle also can continue to be baked to serviceability temperature).
Table 2 is composition analysis results of the pre-melted slag for preparing
Table 1 pre-melted slag proportion scheme
The pre-melted slag composition analysis result that table 2 prepares
(2) use of pro-molten refining slag
Get above-mentioned pre-melted slag, carry out commerical test on 30 tons of LF ladle refining furnaces, technological experiment condition and main economic and technical indices see Table 3, add CaC at molten steel with Al-Si pre-deoxidation and ladle slag
2After the reduction, refining slag is thrown into the molten steel mirror sections, ladle reaches the heating of energising station, refining then, and the major technique performance assessment criteria of molten steel and strand sees Table 3 after the refining.
Table 3 engineer testing condition and main economic and technical indices
From above result as can be known, adopt refining of the present invention after, sulphur, oxygen content and field trash etc. all reach the standard of senior high-quality steel in the steel.Particularly sulphur, phosphorus, oxygen level all reach below the 10ppm, reach the standard of senior Clean Steel, and the Control and Inclusion Removal grade reaches the standard of high-quality, extra best best steel.From refining process, it is all right to change slag, does not have crust and dry slag phenomenon, and ladle slag line position refractory material does not have obvious erosion to be taken place.
Claims (5)
1. the using method of a ultrahigh basicity low aluminum fluorine-free pre-melted type ladle refining slag, described refining slag composition is calculated in mass percent, and CaO 85～95%, B
2O
32～10%, MgO 2～10%, Al
2O
31～10%, impurity in the refining slag should be less than 5%, it is characterized by: be used for LF refining, RH refining and CAS refining, specifically: after liquid steel pre-deoxidizing and the reduction of ladle residue are processed, in the Argon process, pro-molten refining slag dropped into the molten steel mirror sections, molten steel per ton adds the 15kg pre-melted slag, and follow-up refinery practice is identical with the refinery practice of the refining slag that adopts at present routine.
2. the using method of a kind of ultrahigh basicity low aluminum fluorine-free pre-melted type ladle refining slag as claimed in claim 1 is characterized in that: for the LF refining, will drop into ladle behind this pre-melted slag and the blowing agent mixing, reach then the refining of electrical heating station; Or in refining process, throw bag and use.
3. the using method of a kind of ultrahigh basicity low aluminum fluorine-free pre-melted type ladle refining slag as claimed in claim 1, it is characterized in that: for RH refining and CAS refining, behind the ladle argon-blown deslagging, refining slag is dropped into the molten steel mirror sections, fall then dip pipe or cage refining; Or in refining process, throw bag and use.
4. the using method of a kind of ultrahigh basicity low aluminum fluorine-free pre-molten ladle refining slag as claimed in claim 1, it is characterized in that: desulfurization degree reaches 90%, can control the molten steel rephosphorization fully, and sulphur, phosphorus content in the steel are controlled at below 0.0010%.
5. the using method of a kind of ultrahigh basicity low aluminum fluorine-free pre-molten ladle refining slag as claimed in claim 1, it is characterized in that: impurity comprises SiO
2, sulphur and phosphorus and compound thereof.
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|---|---|---|---|
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| CN2009101845964A CN101643822B (en) | 2009-08-31 | 2009-08-31 | Ultrahigh basicity low aluminum fluorine-free refining slag and preparation method and use method thereof |
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| CN101643822B true CN101643822B (en) | 2011-12-21 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051443A (en) * | 2010-12-31 | 2011-05-11 | 昆明理工大学 | High basicity fluorine-free RH (Ruhrstah-Heraeus) desulfurizer |
| CN102719621A (en) * | 2011-03-29 | 2012-10-10 | 鞍钢股份有限公司 | Refining slag prepared from molten steel refining waste slag and method thereof |
| CN102517419A (en) * | 2011-12-21 | 2012-06-27 | 天津钢铁集团有限公司 | Smelting continuous casting method for high carbon steel |
| CN102652989A (en) * | 2012-05-10 | 2012-09-05 | 江苏大学 | Tundish molten steel covering agent for high-cleanness steel pouring and preparation method and application of tundish molten steel covering agent |
| CN102652988A (en) * | 2012-05-10 | 2012-09-05 | 江苏大学 | Boron-containing barium-oxide-base ladle covering agent as well as preparation method and application thereof |
| CN108330336A (en) * | 2018-03-30 | 2018-07-27 | 四川六合锻造股份有限公司 | A kind of high antioxygenic property group of the lanthanides nickel base superalloy and its preparation method and application |
| CN111996335A (en) * | 2020-09-10 | 2020-11-27 | 河北工程大学 | Core-spun yarn core powder composition for high-aluminum steel production and processing method |
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