CN100563871C - A kind of crystallizer protecting cinder for continuous casting of crack sensitive steel and preparation method thereof - Google Patents
A kind of crystallizer protecting cinder for continuous casting of crack sensitive steel and preparation method thereof Download PDFInfo
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- CN100563871C CN100563871C CNB2006100953309A CN200610095330A CN100563871C CN 100563871 C CN100563871 C CN 100563871C CN B2006100953309 A CNB2006100953309 A CN B2006100953309A CN 200610095330 A CN200610095330 A CN 200610095330A CN 100563871 C CN100563871 C CN 100563871C
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- continuous casting
- slag
- covering slag
- crack
- sio
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a kind of crystallizer protecting cinder for continuous casting of crack sensitive steel and preparation method thereof, this covering slag is prepared by wollastonite, lime stone, quartz sand, fluorite, industrial soda, manganese carbonate, carbonaceous material; Its chemical analysis percentage by weight satisfies: CaO 28-42%, SiO
226-40%, CaF
210-20%, Na
2O 4-10%, MnO
22-8%, 0＜Al
2O
3＜6%, C 2-10%; Wherein, ∑ CaO and SiO in the covering slag
2Mass ratio be 1.0-1.2.This crystallizer protecting residue can significantly reduce the infrared radiation heat transfer amount by the slag film, does not increase simultaneously the percent crystallization in massecuite and the crystallization temperature of covering slag, reduces the occurrence probability of the longitudinal crack of casting billet surface, guarantees the continuous casting process direct motion and enhances productivity.This covering slag has the infrared radiation heat transfer ability of good control by the slag film, has good lubricated strand characteristic again, the longitudinal crack of casting billet surface and subcutaneous micro-crack in the time of can significantly reducing continuous casting of crack sensitive steel simultaneously.Its preparation method technology is simple, and is convenient feasible.
Description
Technical field
The present invention relates to molten steel continuous casting steel crystallizer protecting residue, particularly a kind of crystallizer protecting cinder for continuous casting of crack sensitive steel and preparation method thereof, belong to steel-making and continuous casting technology field.
Technical background
Continuous casting steel machine is the main method and the approach of molten steel solidification moulding.In the continuous casting steel machine process, ensure the surface and the internal soundness of continuous casting billet, keep rhythm of production, guarantee that the technology direct motion is the basic demand of casting process.Adopting covering slag at crystallizer during continuous casting is the control cc billet surface quality, guarantees the requisite means of continuous casting direct motion.
At adiabatic heat-insulation that continuous crystallizer protecting slag had, prevent the molten steel secondary oxidation, absorb be mingled with, in several big functions such as lubricated strand and control heat transfer, slag film control strand is vital with the heat transfer of crystallizer and the effect of lubricating casting billet surface and subcutaneous quality.Because the carbon content of steel grade and the difference of alloying element content, the key issue that is faced in the initial stage process of setting in crystallizer is difference to some extent.To mild steel, improve the lubricating ability of covering slag slag film, can improve pulling rate and production efficiency effectively; For high-carbon steel, because elevated temperature strength is low, sticker type breakout easily takes place, improving lubricating ability also is the main task of covering slag; For steel alloy, claimed slag should have the physical and chemical performance stability after good absorption is mingled with, and claimed slag slag film has good lubricating ability simultaneously; For crack sensitive steel (steel grade of [C]=0.09～0.16%), peritectic reaction can take place in the process of setting, the following 50mm of crystallizer meniscus zone initial solidification shell shrinks big, crystal grain is thick, the initial solidification shell growth is inhomogeneous, and when heat flow density was excessive, the slab surface crack index sharply increased, easily crack, this is the main cause of peritectic steel crackle sensitivity.Therefore, weakening on the one hand the heat transfer property of crystallizer, is the main and effective means that solve crack sensitivity steel grade surface quality of continuously cast slab at present by control and the heat-transfer capability that weakens covering slag on the other hand.
At present, both at home and abroad researcher's means of controlling the heat-transfer capability of covering slag adopt the method that improves the covering slag percent crystallization in massecuite to realize substantially.The basicity that improves covering slag can improve the crystallization temperature and the percent crystallization in massecuite of covering slag, and the raising of covering slag basicity has following effect: 1. reduce transparent vitreous body and reduce radiant heat transfer; 2. micropore and the interface in the crystalline solid greatly weakens lattice vibration, thereby weakens conduction heat transfer.But; when covering slag basicity too high; easy severe exacerbation strand lubrication state when recrystallization temperature is too high; cause strand bonding and bleed-out; continuous casting production is forced to adopt the technology path that reduces casting speed; this makes conticaster productivity ratio and production capacity reduce by 20%～30%; thereby the heat-transfer character of research covering slag; particularly how coordinating covering slag slag film lubrication strand conducts heat with control; be related to the key that improves slab quality, improves continuous casting production efficiency, become the hot issue of the continuous casting worker of world today research.
Under normal continuous casting condition of work, the temperature gradient distribution between crystallizer and strand in the slag film is between 300 ℃ and 1200 ℃, and the slag film vertically will be divided into layer liquid and solid layer, and structure of each layer and rheological behavior will influence the lubricated of strand and the influence to conducting heat.The slag film is divided into the two large divisions to the control of conducting heat, and the one, conduction heat transfer, the 2nd, radiant heat transfer, infrared radiation heat transfer account for the ratio of whole heat transfer sometimes up to 40%.
Continuous crystallizer protecting slag commonly used belongs to CaO (CaF
2)-SiO
2-Al
2O
3-Na
2The O-C system, basicity (CaO/SiO
2) roughly between 0.8-1.3.How to pass through the chemical composition of configuration protection slag; change the high temperature rheological behavior and the heat-transfer character of slag film; reach part and reduce slag film infrared radiation heat transfer ability; can guarantee the lubricated slag film heat-transfer capability that can guarantee again to control; enhance productivity when being continuous casting of crack sensitive steel; guarantee cc billet surface quality, guarantee the key problem in technology of continuous casting process direct motion.Given this, (CSTC under support 2006BB4200), carries out relevant rudimentary theoretical research and application study, is key technology solved by the invention place at project of national nature science fund project (50474024) and Chongqing City's natural science fund project.
Summary of the invention
The purpose of this invention is to provide the crystallizer protecting residue that a kind of suitable continuous casting of crack sensitive steel is used; this covering slag has the infrared radiation heat transfer ability of good control by the slag film; simultaneously has good lubricated strand characteristic again, the longitudinal crack of casting billet surface and subcutaneous micro-crack in the time of can significantly reducing continuous casting of crack sensitive steel.
Another object of the present invention provides the method for the described crystallizer protecting residue of preparation.
Purpose of the present invention is achieved through the following technical solutions: a kind of crystallizer protecting cinder for continuous casting of crack sensitive steel, prepared by wollastonite, lime stone, quartz sand, fluorite, industrial soda, manganese carbonate, carbonaceous material etc.; The chemical composition of this crystallizer continuous casting covering slag (weight %) satisfies: CaO 28-42%, SiO
226-40%, CaF
210-20%, Na
2O4-10%, MnO2-8%, 0＜Al
2O
3＜6%, C 2-10%.
For guaranteeing that this covering slag has good crystallization control characteristic, ∑ CaO (comprises CaF in this covering slag
2In Ca) and SiO
2Quality ratio be controlled between the 1.0-1.2; Wherein the chemical composition of raw material (weight %) satisfies respectively:
Wollastonite: SiO
243-53%, CaO 40-49%, 0＜FeO＜1.0%, 0＜S＜0.03%;
Lime stone: CaO 53-55%, 0＜SiO
2＜6.0%, 0＜S＜0.1%;
Quartz sand: SiO
2＞95%;
Fluorite: CaF
285-90%, 0＜SiO
2＜5.0%, 0＜S＜0.05%,
Manganese carbonate: MnCO
3＞96%;
Soda: Na
2CO
3＞95%
Carbonaceous material: C＞95%.
The preparation method of crystallizer protecting cinder for continuous casting of crack sensitive steel comprises following steps:
1) chemical composition of detection raw material silicon lime stone, lime stone, fluorite, quartz sand, manganese carbonate, soda and carbonaceous material;
2) according to the satisfied condition of covering slag chemical composition (weight %), i.e. CaO 28-42%, SiO
226-40%, CaF
210-15%, MnO 2-8%, 0＜Al
2O
3＜6%, calculate required raw-material weight;
3) the above-mentioned wollastonite that takes by weighing in proportion, lime stone, fluorite, quartz sand, manganese carbonate and soda are melted evenly the back cooling naturally of coming out of the stove in the hot stove in ore deposit;
4) fragmentation is worked into about 200 orders;
5) behind the carbonaceous material (C 2-10%) of aequum, in refiner, add 0.8-1.2 normal-temperature water doubly, 2% cellulose binder was finish grinded 30-60 minute, made slip;
6) slurry is sent into spraying granule drying tower inner drying and granulated, product requirement moisture content is less than 0.5%, and granularity packs stand-by less than 2mm.
Compared to existing technology, the present invention has following characteristics:
1) in the continuous casting of molten steel production process; use this crystallizer protecting residue can significantly reduce infrared radiation heat transfer amount by the slag film; do not increase simultaneously the percent crystallization in massecuite and the crystallization temperature of covering slag, reduce the generation probability of the longitudinal crack of casting billet surface, guarantee the continuous casting process direct motion and enhance productivity.
2) continuous crystallizer protecting slag of the present invention is mainly by CaO, SiO
2, Al
2O
3, MnO, Na
2O, CaF
2, C forms.MnO is the chemical constituent that the present invention specially introduces; Discover, MnO has good crystallization control behavior and reduces the ability of infrared energy by the slag film because MnO has weak oxidability, thereby the content of MnO to be limited in 2-6% more appropriate, can give full play to the effect of MnO, not influence the skeleton function of carbonaceous material again.
3) comprehensive basicity (the ∑ CaO/SiO in the continuous crystallizer protecting slag of the present invention
2) be controlled at about 1.0-1.2, can guarantee that the covering slag melt does not at high temperature have strong tendency towards devitrification, thereby can guarantee that the liquid slag layer in the slag film is in the state of Newtonian fluid, fully play the effect of lubricated strand; And solid slag blanket is owing under the intervention effect of MnO, the small CaMnO of part occurs
3Crystal with the infrared optics characteristic stack of MnO itself, has played the effect that reduces the infrared energy transmitance, has reduced the thermograde of base shell section, and the base shell can not be subjected to excessive thermal stress and lobe takes place when having guaranteed continuous casting of crack sensitive steel.
4) contain the CaF of 10%-15% in the continuous crystallizer protecting slag of the present invention
2, at (about 1300 ℃) under the casting temperature condition, CaF
2With other alkalies and alkaline earth oxide (CaO, Na
2O) acting in conjunction makes the liquid slag layer of covering slag slag film keep certain flow behavior, guarantees the lubricating ability of slag film; Contain a certain amount of CaF in the covering slag simultaneously
2, can make the solid slag blanket of slag film separate out cuspidine (Ca under certain conditions
4Si
2O
7F
2), separating out of cuspidine is one of key factor that weakens infrared energy transmitance and conduction heat transfer.
5) require A1 in the covering slag of the present invention
2O
3Content is not more than 5%, and under the continuous casting process condition, the melting in the crystallizer on the molten steel face is protected slag blanket to absorb and assimilated the Al that floats in the molten steel
2O
3Field trash is worked as Al
2O
3Content was less than 20% o'clock, and the rheological behavior of covering slag melting layer can be kept the good ability to the even filling of crystallizer and strand gap, and excellent metallurgical and physical chemistry function.
6) preparation method's technology of the present invention is simple, and is convenient feasible.
The specific embodiment
Embodiment 1:
At first, detect the raw material composition and whether meet the following conditions, and measure the chemical composition of raw material silicon lime stone, lime stone, fluorite, quartz sand, manganese carbonate, soda and carbonaceous material.The raw material that selection meets the following conditions, i.e. wollastonite: SiO
243-53%, CaO40-49%, 0＜FeO＜1.0%, 0＜S＜0.03%; Lime stone: CaO53-55%, 0＜SiO
2＜6.0%, 0＜S＜0.1%; Quartz sand: SiO
2＞95%; Fluorite: CaF
285-90%, 0＜SiO
2＜5.0%, 0＜S＜0.05%, manganese carbonate: MnCO
3＞96%; Soda: Na
2CO
3＞95%; Carbonaceous material: C＞95%; Otherwise, should not use.
Then,, be not difficult to calculate required raw-material weight, see Table 2 according to the chemical composition of covering slag such as the condition of table 1;
Covering slag of the present invention adopts following technique process refining: the above-mentioned wollastonite that takes by weighing in proportion, lime stone, fluorite, quartz sand, manganese carbonate and soda are melted evenly the back cooling naturally of coming out of the stove in the hot stove in ore deposit; Fragmentation is worked into 200 orders; After the amount of carbonaceous material represented (as carbon black 2% and high-carbon graphite 4%) as table one, in refiner, add 0.8-1.2 normal-temperature water doubly, 2% cellulose binder is (as CMC: CMC), finish grinded 30-60 minute, make slip; Slurry is sent into spraying granule drying tower inner drying granulate, product requirement moisture content is less than 0.5%, and granularity is less than 2mm, and the sealing pack is stand-by.
Chemical composition, the physical property of covering slag see Table 1, and the raw material weight ratio sees Table 2, and corresponding casting steel grades sees Table 3.
Chemical composition of table 1 continuous casting covering slag (w%) and physical property (1300 ℃)
Table 2 fritting raw material weight ratio
The chemical composition of the corresponding steel of table 3
Experiment condition is: sheet billet continuous casting, and casting blank section: 200 * 1250mm, pulling rate: 0.7-1.30m/min waters steel temperature: 1525-1545 ℃.The percent crystallization in massecuite of covering slag is about 50%.Compare with former use covering slag, the longitudinal crack ratio reduces about 20%.
Embodiment 2:
Its method is identical with embodiment 1; the raw material of covering slag also are wollastonite, lime stone, fluorite, quartz sand, manganese carbonate, soda and carbonaceous material; chemical composition, the physical property of covering slag see Table 4; fritting raw material weight ratio sees Table 5; with addition of carbonaceous material be: 2% carbon black; 6.4% high-carbon graphite, corresponding composition of steel sees Table 6.
Chemical composition of table 4 covering slag (%) and physical property (1300 ℃)
Table 5 fritting raw material weight ratio
The chemical composition of the corresponding steel of table 6
Experiment condition is: sheet billet continuous casting, and casting blank section: 200 * 1250mm, 240 * 1400mm, pulling rate: 0.7-1.30m/min waters steel temperature: 1525-1545 ℃.The percent crystallization in massecuite of covering slag is compared with former use covering slag about 50%, and the strand longitudinal crack significantly reduces, because the removing surface rate that longitudinal crack causes reduces by 50%, but this slag system scale is used for industrial production.
Embodiment 3:
Its method is identical with embodiment 1; the raw material of covering slag also are wollastonite, lime stone, fluorite, quartz sand, manganese carbonate, soda and carbonaceous material; chemical composition, the physical property of covering slag see Table 7; the raw material weight ratio sees Table 8; with addition of carbonaceous material be: 2% carbon black; 5.3% high-carbon graphite, the composition of corresponding steel sees Table 9.
Chemical composition of table 7 covering slag (wt%) and physical property (1300 ℃)
Table 8 fritting raw material weight ratio
The corresponding test of table 9 chemical composition of steel
Experimental condition is: slab caster, and casting blank section: 240 * 1400mm, 170 * 1000mm, 180 * 1000mm, casting speed are 0.7-1.3m/min; Pouring temperature: 1525-1545 ℃, not only to avoid occurring surface longitudinal crack during this class steel grade continuous casting, also to avoid the surface and the generation of subcutaneous micro-crack, thereby when casting this class steel grade, need suitably to reduce the basicity of covering slag, this test basicity of slag (∑ CaO/SiO
2) being reduced to 1.0, percent crystallization in massecuite is less than 30%; By improving the fusion temperature and the viscosity of covering slag, increase the slag film thickness simultaneously, add a certain amount of MnO simultaneously, reach the function that weakens heat transfer to regulate the projection that the slag film is separated out crystallite and reduced infrared waves.Test find this covering slag coordinate to conduct heat and lubricated aspect obtain good effect, surface longitudinal crack of slab and micro-crack all descend, and are reduced to below 0.2% because the stocking that crizzle causes moves back useless rate, for the continuous casting process direct motion provides assurance.
The present invention is on the basis of traditional high alkalinity continuous casting covering slag, and ∑ CaO/SiO is controlled in strictness
2Ratio, make it between 1.0-1.2; The special transition group metallic oxide MnO that adds; make this covering slag under the condition that does not significantly improve basicity and percent crystallization in massecuite; ability with the infrared heat transfer of good control and conduction heat transfer, because basicity is not high, percent crystallization in massecuite is lower; lubricating ability is stronger; can guarantee when the casting crack sensitive steel, to weaken the thermal stress and the resistance of billet withdrawal of casting blank shell, thereby alleviate the generation of longitudinal crack and the appearance of micro-crack; guarantee the direct motion of continuous casting process, and guaranteed stabilizing and increasing of pulling rate.
Experimental studies have found that, in slag system involved in the present invention, as basicity ∑ CaO/SiO
2Be controlled at about 1.0-1.2, the crystallizing power of slag system and tendency can be controlled by other components, can satisfy the i.e. control heat transfer purpose of lubricated strand again; Basicity is low excessively, and covering slag crystallization difficulty is not easy control and conducts heat, and basicity is too high, and the crystallization hyperenergia will have a strong impact on the lubrication property of covering slag, so in the present invention with basicity ∑ CaO/SiO
2Be controlled at about 1.0-1.2.
Contain the MnO component in the covering slag; no matter be at crystalline state or at glassy state; the effect of remarkable reduction infrared radiation heat transfer is all arranged; MnO controls the effect that crystallite is separated out in addition simultaneously; thereby the covering slag with such component can conduct heat under the condition of low percent crystallization in massecuite in control, but MnO has weak oxidation susceptibility, and too high levels also has the tendency of excessive promotion crystallization; so in the present invention, MnO content is controlled in the 2-8%.
Claims (2)
1, a kind of crystallizer protecting cinder for continuous casting of crack sensitive steel is characterized in that: prepared by wollastonite, lime stone, quartz sand, fluorite, industrial soda, manganese carbonate, carbonaceous material; The chemical component weight percentage of this crystallizer continuous casting covering slag satisfies: CaO 28-42%, SiO
226-40%, CaF
210-20%, Na
2O 4-10%, MnO 2-8%, 0＜Al
2O
3＜6%, C 2-10%;
Wherein, comprehensive basicity ∑ CaO and SiO in the covering slag
2Mass ratio be 1.0-1.2.
2, according to the preparation method of the described crystallizer protecting cinder for continuous casting of crack sensitive steel of claim 1, comprise following steps:
1) chemical analysis of detection raw material silicon lime stone, lime stone, fluorite, quartz sand, manganese carbonate, soda and carbonaceous material;
2) condition that satisfies according to covering slag chemical component weight percentage, i.e. CaO 28-42%, SiO
226-40%, CaF
210-15%, MnO 2-8%, 0＜Al
2O
3＜6%, calculate required raw-material weight;
3) take by weighing wollastonite, lime stone, fluorite, quartz sand, manganese carbonate and soda according to the above ratio, and fusing is cooled off naturally after coming out of the stove evenly in the hot stove in ore deposit;
4) fragmentation is worked into 200 orders;
5) behind the carbonaceous material of aequum, in refiner, add 0.8--1.2 times normal-temperature water and 2% cellulose binder, finish grinded 30-60 minute, make slurry;
6) slurry is sent into spraying granule drying tower inner drying and granulated, product requirement moisture content is less than 0.5%, and granularity packs stand-by less than 2mm.
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|---|---|---|---|
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|---|---|---|---|
| CNB2006100953309A CN100563871C (en) | 2006-12-22 | 2006-12-22 | A kind of crystallizer protecting cinder for continuous casting of crack sensitive steel and preparation method thereof |
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| CN100563871C true CN100563871C (en) | 2009-12-02 |
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