CN101332497A - Continuous casting protection slag for high-alumina steel and manufacture method thereof - Google Patents

Continuous casting protection slag for high-alumina steel and manufacture method thereof Download PDF

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CN101332497A
CN101332497A CNA2007100425406A CN200710042540A CN101332497A CN 101332497 A CN101332497 A CN 101332497A CN A2007100425406 A CNA2007100425406 A CN A2007100425406A CN 200710042540 A CN200710042540 A CN 200710042540A CN 101332497 A CN101332497 A CN 101332497A
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slag
cao
continuous casting
steel
manufacture method
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CN101332497B (en
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朱祖民
张晨
蔡得祥
庄铁
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Baoshan Iron and Steel Co Ltd
Baosteel Group Corp
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Baoshan Iron and Steel Co Ltd
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Abstract

The invention relates to a steel-making auxiliary material and a production method thereof, in particular to a continuous casting powder for high-aluminum steel and a production method thereof. The invention is mainly technically characterized in that the casting powder raw material is prepared by using the following chemical components with the percentage: CaO+Al2O3 accounts for 50%-60%, and the ratio of CaO to Al2O3 is 0.7-1.3, SrO accounts for 4-10%, BaO accounts for 2-5%, MgO accounts for 1-3%, fluxing agent is composed of Na2O which accounts for 10-16%, Li2O accounting for 2-5%, F accounting for 6-12%, and SiO2 which is kept less than or equal to 2%. The casting powder is produced by the steps of melting, water quenching, drying and crushing and by adding a carbon material. The continuous casting powder can inhibit the oxidized strong reducing elements from entering the slag to cause the slag denaturation; and can ensure smooth continuous casting production of steel products containing high aluminum, Ti and rare earths, and good surface quality of casting blank.

Description

A kind of continuous casting protection slag for high-alumina steel and manufacture method thereof
Technical field
The present invention relates to make steel auxiliary material and manufacture method thereof, particularly a kind of continuous casting protection slag for high-alumina steel and manufacture method thereof.
Background technology
When molten steel casts continuously, constantly add covering slag on the molten steel face in continuous cast mold, the covering slag of fusing plays effect lubricated and that control is conducted heat along with the vibration of crystallizer constantly flows between strand and the crystallizer; The slag secluding air is avoided molten steel oxidation; Rong solid slag does not have insulation effect to molten steel; Slag also absorbs the field trashes such as aluminium oxide in the molten steel.The main chemical composition of covering slag is CaO, SiO 2And Al 2O 3Deng, add subcarbonate and fluoride again to regulate fusing point, viscosity, add carbon material and regulate burn-off rate.SiO as one of main component 2Content in the covering slag slag is 30%～50%.(SiO in the slag 2) slag steel interface can and molten steel in Strong reducing metal element chemically reactive, for example: 4[Al]+3 (SiO 2) → 2 (Al 2O 3)+3[Si] reaction the result be Al 2O 3Enter slag, Si has entered molten steel.If also contain titanium elements, rare earth metal element in the molten steel then also similar chemical reaction can take place.This shows the Al in the slag 2O 3Increment partly forms by two: the Al that floats in the absorption molten steel 2O 3The Al that field trash and the reaction of slag steel generate 2O 3.The Al in the slag generally 2O 3Increment 3%～6%, aluminum killed steel is higher than aluminium-silicon killed steel.Al in the slag 2O 3Increment can produce some influences to Slag Properties, but considered this factor during the performance design of covering slag, so generally what problem can not occur.
As the Al in the molten steel, Ti, when rare earth element content is higher, the oxide of these elements enters slag more for a long time, can worsen the performance of slag.For example when [Al] content in the molten steel greater than＞1% the time, the Al in the slag 2O 3Increment＞15% (greatly partly be [Al] and (SiO of slag in the molten steel 2) reacted product), the SiO in the slag 2Decrement be greater than 13%, can generate 2CaO.Al 2O 3.SiO 2High-melting-point mineral (cacoclasite), promote the fusing point and the viscosity of slag, slag can not balancedly flow between crystallizer and the strand, cc billet surface quality worsens, and continuous casting can not be proceeded, even the bleed-out accident occurs.Equally, the oxide of Ti, rare earth element in slag excessively enrichment also can promote the fusing point, viscosity of slag and the similar problem that causes.For this class Al, Ti, the higher steel grade of rare earth element content, common continuous casting covering slag obviously is inapplicable.
When patent KR-2005041475 contains the above ferrite stainless steel continuous casting in Ti＞0.4 in order to solve because of SiO in the slag 2Make slag loss SiO with the Ti reaction in the molten steel 2Thereby, make CaO/SiO 2Sharply rise, influence is lubricated to strand, thereby with the initial CaO/SiO of slag 2Designing lowlyer, is 0.6～0.7, makes the final CaO/SiO of slag 2Be not more than 1.0.But this equals to have improved (SiO in the slag 2) activity, promoted (SiO in the slag 2) with molten steel in the reaction of elements such as [Al].
Patent JP-57184563 is with the SiO in the covering slag 2Be limited in below 7%, control CaO content is 40～60%, Al 2O 3Content is 20～40%.This covering slag is by what SiO 2Low, glass is poor, the fusion temperature height, and the addition of flux is big, and particularly the addition of element F pollutes the environment etching apparatus after improving.
Summary of the invention
The purpose of this invention is to provide a kind of continuous casting protection slag for high-alumina steel and manufacture method thereof; suppressing above-mentioned strong reducing property element enters slag after oxidized and makes the slag sex change; solution contains high Al, Ti and terres rares has the continuous casting problem of strong reducing property element steel; thereby make this class steel grade continuous casting production direct motion, cc billet surface quality is good.
The technical scheme that the present invention addresses the above problem is:
A kind of continuous casting protection slag for high-alumina steel, its chemical composition per distribution ratio is: CaO+Al 2O 3%:50%～60%, and CaO%/Al 2O 3%=0.7～1.3, SrO:4～10%, BaO:2～5%, MgO:1～3%, flux: Na 2O:10～16%, Li 2O:2～5%, F:6～12%, and keep SiO 2≤ 2%.
CaO and Al in the covering slag of the present invention 2O 3Be Main Ingredients and Appearance, common (CaO+Al 2O 3) % is greater than 50%, and CaO%/Al 2O 3This requirement of %=0.7～1.3 is according to CaO-Al 2O 3Phasor and come.Work as CaO%/Al from phasor 2O 3%=0.7～1.3 o'clock just the vitrifying of calcium aluminate form the district, are the low melting point districts.Work as CaO%/Al 2O 3% approaches 1 o'clock CaO-Al just 2O 3Eutectic point, this position fusing point is minimum.
SrO, BaO, MgO can play the Al in slag absorption molten steel 2O 3Keep the effect of the stability of its viscosity behind the field trash, secondly from " multicomponent melange effect ", the constituent element of covering slag is many more, and fusing point is low more.The content of SrO reduces the effect of fusing point, viscosity when 4～10% scopes the most remarkable, and it is not remarkable that BaO, MgO reduce the effect of fusing point, viscosity, so addition is less.
The flux Na that adds an amount of adjustment covering slag physical property 2O, Li 2O and F, these fluxs also are indispensable parts in the covering slag composition.Under the condition of the aforesaid constituent element addition of covering slag, if Na 2O is higher and inapplicable less than 10% covering slag fusing point, Na 2O is low excessively greater than 16% fusing point.Li 2O has and reduces slag fusing point, viscosity effect, vitrified effect of promotion is arranged again, but cost an arm and a leg, it and Na 2The optimum Match addition of O is 2～5%.F is a most important element of adjusting covering slag viscosity, and in covering slag of the present invention, the addition of F was less than 6% o'clock, and viscosity is regulated not in place, and not only viscosity was on the low side greater than 12% o'clock, and F is too high can impact environment.
Bring the unavoidable impurities SiO in the covering slag into 2Total amount reduces the SiO in the covering slag less than 2% 2Content can reduce SiO in the slag 2Activity, weaken the oxidisability of slag.
Preferably, described CaO%/Al 2O 3% ≈ 1.Experimental study has confirmed to add composition outside, add under the identical condition of flux, works as CaO%/Al 2O 3The fusion temperature that % approaches 1 o'clock covering slag is minimum, therefore, and CaO%/Al 2O 3% ≈ 1 is optimal.
A kind of manufacture method of continuous casting protection slag for high-alumina steel may further comprise the steps:
(1) prepares raw material: CaO+Al by following chemical composition per distribution ratio 2O 3%:50%～60%, and CaO%/Al 2O 3%=0.7～1.3, SrO:4～10%, BaO:2～5%, MgO:1～3%, and keep unavoidable impurities SiO 2Total amount is less than 2%.The flux proportioning of regulating the covering slag performance is: Na 2O:10～16%, Li 2O:2～5%, F:6～12%;
(2) fusing can be with lining-less water cooled furnace wall furnace melting under greater than the temperature of covering slag fusion temperature more than 200 ℃, as being that thermal source melts inaccessible SiO with the coke with the lining-less shaft furnace 2Total amount is less than 2% target;
(3) shrend, slag directly enter normal temperature pond cooled and solidified and become vitreum;
(4) drying is prepared moisture oven dry for next step pulverizing less than 2% for water content;
(5) pulverize;
(6) add 2～4% carbon materials, make by various device Powdered, graininess or hollow spheres covering slag, the effect of carbon material is the burn-off rate of regulating covering slag.
Preferably, in the described step (6), carbon materials is graphite and carbon black, uses simultaneously to well with two kinds of materials.
Preferably, in the described step (5), the powder size after the pulverizing is that screenings 80% is by being at least 200 mesh sieve.
The present invention compared with prior art has following beneficial effect:
1. can solve and contain high Al, Ti and terres rares has the continuous casting problem of strong reducing property element steel, suppress above-mentioned strong reducing property element and enter slag after oxidized and make the slag sex change.
2. improve the composition of covering slag, contain the steel grade continuous casting production direct motion that high Al, Ti and terres rares have the strong reducing property element thereby make, no bleed-out alarm condition takes place, and cc billet surface quality is good.
Description of drawings
Fig. 1 is CaO-Al 2O 3Phasor.
Fig. 2 is CaO and Al 2O 3Reciprocation schematic diagram to fusion temperature.
Fig. 3 is the activity schematic diagram of silica.
The specific embodiment
Embodiment 1
A kind of continuous casting protection slag for high-alumina steel, its chemical composition per distribution ratio is: CaO+Al 2O 3%:58% and CaO%/Al 2O 3%=0.93, SrO:12%, BaO:3%, MgO:1%, flux: Na 2O:10%, Li 2O:3%, F:8%, and keep SiO 2≤ 2%.In the raw material proportioning, must make the unavoidable impurities SiO that brings in the covering slag 2Total amount is less than 2%.Reduce the SiO in the covering slag 2Content can significantly reduce SiO in the slag 2Activity, weaken the oxidisability of slag greatly, the activity of silica as shown in Figure 3.
Make the manufacture method of above-mentioned continuous casting protection slag for high-alumina steel, may further comprise the steps:
(1) prepares raw material: CaO+Al by following chemical composition per distribution ratio 2O 3%:58% and CaO%/Al 2O 3%=0.93, SrO:12%, BaO:3%, MgO:1%, the flux proportioning is: Na 2O:10%, Li 2O:3%, F:8%, and keep SiO 2≤ 2%;
(2) fusing is with lining-less water cooled furnace wall furnace melting;
(3) shrend, slag directly enter the pond and are frozen into vitreum;
(4) drying is with the moisture oven dry, for pulverizing is prepared;
(5) pulverize, the powder size after the pulverizing is that screenings 80% is by 200 orders;
(6) graphite and the carbon black material of adding 2.2% are made covering slag.
Embodiment 2
A kind of continuous casting protection slag for high-alumina steel, its chemical composition per distribution ratio is: CaO+Al 2O 3%:55% and CaO%/Al 2O 3%=0.72, SrO:10%, BaO:2%, MgO:3%, flux: Na 2O:14%, Li 2O:2%, F:7%, and keep SiO 2≤ 2%.
Make the manufacture method of above-mentioned continuous casting protection slag for high-alumina steel, may further comprise the steps:
(1) prepares raw material: CaO+Al by following chemical composition per distribution ratio 2O 3%:55% and CaO%/Al 2O 3%=0.72, SrO:10%, BaO:2%, MgO:3%; The flux proportioning is: Na 2O:14%, Li 2O:2%, F:7%, and keep SiO 2≤ 2%;
(2) fusing is with lining-less water cooled furnace wall furnace melting;
(3) shrend, slag directly enter the pond and are frozen into vitreum;
(4) drying is with the moisture oven dry, for pulverizing is prepared;
(5) pulverize, the powder size after the pulverizing is that screenings 80% is by 200 orders;
(6) graphite and the carbon black material of adding 3.6% are made covering slag.
Embodiment 3
As CaO-Al 2O 3Series protection slag, in the present embodiment, CaO and Al in the covering slag 2O 3Be Main Ingredients and Appearance, common (CaO+Al 2O 3) % is greater than 50%, works as CaO%/Al from phasor 2O 3%=0.7～1.3 o'clock just the vitrifying of calcium aluminate form the district, are the low melting point districts.And work as CaO%/Al 2O 3% approaches 1 o'clock CaO-Al just 2O 3Eutectic point, this position fusing point is minimum.Therefore, CaO%/Al 2O 3% ≈ 1 is optimal, as shown in Figure 1.Experimental study has confirmed to add composition outside, add under the identical condition of flux, works as CaO%/Al 2O 3The fusion temperature that % approaches 1 o'clock covering slag is minimum, as shown in Figure 2.Therefore, in the present embodiment, according to CaO%/Al 2O 3% ≈ 1 is made into covering slag raw material: CaO+Al 2O 3%:58% and CaO%/Al 2O 3%=1, SrO:5%, BaO:5%, MgO:2%, flux: Na 2O:12%, Li 2O:3%, F:9%, and keep SiO 2≤ 2%.
Make the manufacture method of above-mentioned continuous casting protection slag for high-alumina steel, may further comprise the steps:
(1) prepares raw material: CaO+Al by following chemical composition per distribution ratio 2O 3%:55% and CaO%/Al 2O 3%=1, SrO:5%, BaO:5%, MgO:2%; The flux proportioning is: Na 2O:12%, Li 2O:3%, F:9%; And maintenance SiO 2≤ 2%;
(2) fusing is with lining-less water cooled furnace wall furnace melting;
(3) shrend, slag directly enter the pond and are frozen into vitreum;
(4) drying is with the moisture oven dry, for pulverizing is prepared;
(5) pulverize, the powder size after the pulverizing is that screenings 80% is by 200 orders;
(6) graphite and the carbon black material of adding 3% are made covering slag.
Embodiment 4
A kind of continuous casting protection slag for high-alumina steel, its chemical composition per distribution ratio is: CaO+Al 2O 3%:57% and CaO%/Al 2O 3%=1.28, SrO:8%, BaO:4%, MgO:1%, flux: Na 2O:16%, Li 2O:5%, F:12%, and keep SiO 2≤ 2%.
Make the manufacture method of above-mentioned continuous casting protection slag for high-alumina steel, may further comprise the steps:
(1) prepares raw material: CaO+Al by following chemical composition per distribution ratio 2O 3%:57% and CaO%/Al 2O 3%=1.28, SrO:8%, BaO:4%, MgO:1%; The flux proportioning is: Na 2O:16%, Li 2O:5%, F:12%; And maintenance SiO 2≤ 2%;
(2) fusing is with lining-less water cooled furnace wall furnace melting;
(3) shrend, slag directly enter the pond and are frozen into vitreum;
(4) drying is with the moisture oven dry, for pulverizing is prepared;
(5) pulverize, the powder size after the pulverizing is that screenings 80% is by 200 orders;
(6) graphite and the carbon black material of adding 2.6% are made covering slag.
Table 1 is relatively tabulated for covering slag in 4 embodiment of the present invention and the prior art uses the result
Table 1
Figure A20071004254000081
Figure A20071004254000091

Claims (5)

1. a continuous casting protection slag for high-alumina steel is characterized in that its chemical composition per distribution ratio is: CaO+Al 2O 3%:50%～60%, and CaO%/Al 2O 3%=0.7～1.3, SrO:4～10%, BaO:2～5%, MgO:1～3%, flux: Na 2O:10～16%, Li 2O:2～5%, F:6～12%, and keep SiO 2≤ 2%.
2. continuous casting protection slag for high-alumina steel as claimed in claim 1 is characterized in that: described CaO%/Al 2O 3% ≈ 1.
3. the manufacture method of a continuous casting protection slag for high-alumina steel is characterized in that may further comprise the steps:
(1) prepares raw material: CaO+Al by following chemical composition per distribution ratio 2O 3%:50%～60%, and CaO%/Al 2O 3%=0.7～1.3, SrO:4～10%, BaO:2～5%, MgO:1～3%, flux: Na 2O:10～16%, Li 2O:2～5%, F:6～12%, and keep SiO 2≤ 2%;
(2) fusing can be carried out under greater than the temperature of covering slag fusion temperature more than 200 ℃;
(3) shrend, slag directly enter normal temperature pond cooled and solidified and become vitreum;
(4) drying is that water content is less than 2%, for next step pulverizing is prepared with the moisture oven dry;
(5) pulverize;
(6) carbon materials of adding 2～4% is made covering slag.
4. the manufacture method of continuous casting protection slag for high-alumina steel as claimed in claim 3 is characterized in that in the described step (6), described carbon materials is graphite and carbon black.
5. the manufacture method of continuous casting protection slag for high-alumina steel as claimed in claim 3 is characterized in that in the described step (5), and the powder size after the pulverizing is that screenings 80% is by being at least 200 mesh sieve.
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CN109060699B (en) * 2018-09-27 2021-02-23 广西大学 Method for measuring vitreous body content of industrial water-quenched slag
CN109175287A (en) * 2018-11-05 2019-01-11 首钢集团有限公司 A kind of high-aluminum steel sheet billet continuous casting method
CN114029462A (en) * 2021-11-15 2022-02-11 东北大学 Rare earth oxide-containing continuous casting mold flux for high-titanium low-aluminum steel and preparation method thereof
CN114029462B (en) * 2021-11-15 2023-03-28 东北大学 Rare earth oxide-containing continuous casting mold flux for high-titanium low-aluminum steel and preparation method thereof
CN114054699A (en) * 2021-11-22 2022-02-18 武汉科技大学 High-manganese low-temperature steel continuous casting crystallizer casting powder
CN114713782A (en) * 2022-05-10 2022-07-08 江苏嘉耐高温材料股份有限公司 Pre-melted crystallizer casting powder for rare earth stainless steel and preparation method thereof
CN114713782B (en) * 2022-05-10 2024-04-02 江苏嘉耐高温材料股份有限公司 Premelting crystallizer covering slag for rare earth stainless steel and preparation method

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