CN101125357A - Continuous casting crystallizer protective scoria for weathering steel and manufacturing method thereof - Google Patents

Continuous casting crystallizer protective scoria for weathering steel and manufacturing method thereof Download PDF

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Publication number
CN101125357A
CN101125357A CNA2007102017505A CN200710201750A CN101125357A CN 101125357 A CN101125357 A CN 101125357A CN A2007102017505 A CNA2007102017505 A CN A2007102017505A CN 200710201750 A CN200710201750 A CN 200710201750A CN 101125357 A CN101125357 A CN 101125357A
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continuous casting
scoria
covering slag
weathering steel
percent
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CN100528406C (en
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陈天明
杨素波
段大福
曾建华
张均祥
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Pangang Group Steel Vanadium and Titanium Co Ltd
Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
Panzhihua New Steel and Vanadium Co Ltd
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Abstract

The present invention relates to a continuous casting mold protecting powder and the manufacturing method of the mold protecting powder for a weathering steel. Adopting the making art of spraying particle, the mold protecting powder is made from the materials such as premelting material, quartz sand, fluorite, industrial calcined soda, magnesite, medium supper soot carbon, graphite, lithium carbonate and so on, chemical ingredients of the mold protection powder in weight percentage are as follows: SiO2 30.0 to 37.0 percent, CaO 30.0 to 37.0 percent, Al2O3 2.0 to 5.0 percent, MgO 3.0 to 6.0 percent, Li2O 1.5 to 2.5 percent, Na2O 5.5 to 8.5 percent, F 4.5 to 7.5 percent, TC(totally carbon) 4.5 to 6.5 percent, 0< Fe2O3 less than or eqal to 1.0%, binary alkalinity CaO/SiO2 is 0.95 to 1.05. The mold protecting powder regarding the invention melts evenly inside the mold and has weak reaction with the rare earth wire, excellent lubricating performance to the casting blank, even and proper heat transmission between the continuous casting mold and the casting blank, therefore reducing the ingot bleeding rate and the occurance rate of surface vertical flaws.

Description

A kind of continuous casting crystallizer protective scoria for weathering steel and manufacture method thereof
Technical field:
The present invention relates to a kind of molten steel continuous casting steel crystallizer protecting residue, particularly a kind of weathering steel crystallizer protecting cinder for continuous casting and preparation method thereof belongs to steel-making and continuous casting technology field.
Technical background:
Weathering steel (comprising steel grades such as 09CuPRE, 09CuPTiRE, 09CuPCrNi) is owing to contain the responsive element of crackles such as Cu, Ti, Cr and Ni, and casting billet surface is easy to generate defectives such as crackle, pit in the casting process.In the casting process, adopting covering slag at crystallizer is the control surface quality of continuously cast slab, guarantees the requisite means of continuous casting direct motion.The main effect of crystallizer protecting residue is as follows: 1, lubricate between crystallizer and strand; 2, absorb the field trash that from molten steel, floats up; 3, prevent a secondary oxidation and an insulation effect of molten steel; 4, control from solidified shell to the heat transfer rate of crystallizer etc.Wherein the heat transfer of crystallization control device and strand with lubricated be vital to casting billet surface and subcutaneous mass action.
Usually take the process of feeding rare-earth wires in crystallizer that it is carried out degenerative treatments for the sulfide that is mingled with in the molten steel, and reach the purpose of cleaning molten steel.Because rare earth element is more active, easy and Na when passing the covering slag liquid slag layer 2O, SiO 2React, generate unsettled low price rare earth oxide, will be reduced at high temperature and generate stable high price rare earth oxide and the rare earth silicate that is difficult to ionization.The rare earth oxide fusing point is very high, all more than 2000 ℃, if covering slag is relatively poor to its solvability, then has high-melting-point materials such as the composite oxides existence that rare earth oxide or itself and covering slag constituent element form in the slag.These high-melting-points float mutually, make the surface conglomeration of slag film, or form the slag bar on crystallizer wall, hinder the even inflow of melt cinder.The high-melting-point that does not partly float is very easily separated out crystal after entering the slag film in addition, and the lubricated and uniformly transfer heat effect of slag film is damaged like this, brings out slab surface crack and produces, and causes the bleed-out accident in the time of seriously.In a word, Feeding Rare Earth Wire in Continuous Casting Mould technology can cause that fusing point, viscosity, basicity, recrystallization temperature, the setting temperature of covering slag significantly change, and causes its serviceability to worsen.
In existing technology, by changing the covering slag composition, can make it to react with rare-earth wires less as far as possible, can dissolve rare earth oxide fast, in large quantities simultaneously, and form uniform glassy phase.Concrete measure mainly contains following several: (1) covering slag reduces Na 2O, SiO 2Content, increase Al 2O 3To reduce the generation of rare earth oxide; (2) increase B 2O 3Make flux Deng constituent element, and improve the ability of dissolving rare earth oxide; (3) increase constituent element K in right amount 2O improves the covering slag melting characteristic, the double as flux; (4) adopt higher alkalisation (CaO/SiO 2), this ratio can improve the crystallization temperature and the percent crystallization in massecuite of covering slag generally more than 1.1, reduces on the one hand radiant heat transfer, and the heat-transfer intensity that can hinder and decay of fine crack, the space in the crystalline solid on the other hand reaches to slow down and conducts heat and the purpose of minimizing crackle.Usually also contain 1～2.5% Fe in the covering slag 2O 3, can accelerate the carbonaceous material scaling loss, reduce sinter layer thickness.But because Fe 2O 3Have oxidisability, can react, make covering slag middle rare earth oxide quicken to generate with rare-earth wires.
In addition, when covering slag basicity is too high, cause its recrystallization temperature too high easily, thereby severe exacerbation strand lubrication state cause strand bonding and bleed-out.Continuous casting production is forced to adopt the technology path that reduces casting speed, makes conticaster productivity ratio and production capacity reduce by 20%～30%.Basicity is crossed low then covering slag crystallization difficulty, is not easy control and conducts heat.
Therefore study the lubricated and heat transfer property of covering slag; particularly how to pass through the chemical composition of configuration protection slag; change its high temperature rheological behavior and heat-transfer character; can guarantee the lubricated heat-transfer capability that can guarantee to control again; enhance productivity when being the weathering steel continuous casting; guarantee cc billet surface quality, guarantee the key problem in technology of continuous casting process direct motion.
Summary of the invention:
The purpose of this invention is to provide a kind of weathering steel crystallizer protecting cinder for continuous casting.This covering slag melts in crystallizer evenly, and is good to lubricating of strand, and the heat transfer between crystallizer and strand evenly, suitably.
Purpose of the present invention is achieved through the following technical solutions: a kind of weathering steel crystallizer protecting cinder for continuous casting, by pre-melt, quartz sand, fluorite, calcined soda for industry, magnesia, in material such as super carbon black, graphite, lithium carbonate prepared.The pre-molten material for continuous crystallizer protecting slag finished product of wherein pre-melt for buying mainly is made up of lime stone, quartz sand, fluorite, calcined soda for industry.
The chemical composition of this crystallizer protecting residue contains by weight percentage: SiO 230.0～37.0%, CaO 30.0～37.0%, Al 2O 32.0～5.0%, MgO 3.0～6.0%, Li 2O 1.5～2.5%, Na 2O 5.5～8.5%, F 4.5～7.5%, TC (full carbon) 4.5～6.5%, 0＜Fe 2O 3≤ 1.0%, all the other are K 2O≤2%, MnO≤1% and other micro-component.
In order to guarantee that this covering slag is good to lubricating of strand, has the ability of conducting heat between crystallization control device and strand concurrently, dual alkalinity CaO/SiO in this covering slag simultaneously 2Quality ratio be controlled between 0.95～1.05.
The physicochemical property parameter of crystallizer protecting residue of the present invention is: hemisphere point fusion temperature: 1090～1150 ℃; Viscosity under 1300 ℃: 0.17～0.27Pas; Recrystallization temperature: 900～960 ℃; Setting temperature: 920～980 ℃.
Further, the chemical composition of crystallizer protecting residue of the present invention is preferably (by weight percentage): SiO 230.7～36.4%, CaO 31.8～36.1%, Al 2O 32.8～4.9%, MgO 3.3～5.7%, Li 2O 1.6～2.5%, Na 2O 5.8～8.3%, F 4.9～7.0%, TC (full carbon) 4.8～6.4%, 0＜Fe 2O 3≤ 1.0%, all the other are K 2O≤2%, MnO≤1% and other micro-component.Covering slag in the preferable range has the ability of good lubricating property and control heat transfer.
Another object of the present invention provides the method for the described crystallizer protecting residue of preparation.
The preparation method of weathering steel crystallizer protecting cinder for continuous casting is as follows:
1, detects raw material: the chemical composition of pre-melt, quartz sand, fluorite, calcined soda for industry, magnesia, lithium carbonate, carbonaceous material;
2, will cross 180 mesh sieves after pre-melt, quartz sand, the fluorite fragmentation, cross 320 mesh sieves after the magnesia fragmentation;
3,, calculate the weight of needed raw material according to the satisfying condition of covering slag chemical composition;
4, take by weighing above-mentioned raw materials premix in the twin-screw mixing procedure machine in proportion, send into to stir in the mill and make slurry;
5, slurry is imported pans, send into mist projection granulating in the spray tower by high-pressure pump.
Crystallizer protecting residue moisture content of finished products of the present invention≤0.50%, granularity＜2.0mm.Granularity 0.2～1.0mm level 〉=80% wherein is less than 0.2mm level＜15%.In preferred particle size range, crystallizer protecting residue can well be implemented the effect that it is sprawled and is incubated, and makes the fusion of this covering slag, greasy property reach optimal effectiveness.
Compared to existing technology, the present invention has following characteristics:
1) contains lower Fe 2O 3Component: the present invention has reduced the Fe that has oxidisability in the covering slag 2O 3Content, during the liquid slag layer of rare-earth wires high temperature in passing crystallizer, oxidation reaction weakens, and has reduced the generation of covering slag middle rare earth oxide, has reduced the enrichment of covering slag use middle rare earth oxide in one aspect.
2) has low CaO/SiO 2Ratio: the present invention has suitably reduced CaO/SiO on the basis of traditional high alkalinity covering slag 2Ratio, make it between 0.95～1.05, it is too high to have overcome in the existing covering slag composition basicity, causes its recrystallization temperature too high easily, thereby severe exacerbation strand lubrication state causes problems such as strand bonding and bleed-out.
3) added Li especially 2O, MgO: make this covering slag under the condition that does not significantly improve basicity and percent crystallization in massecuite, reduced the recrystallization temperature and the setting temperature of covering slag.
Show through site test results; this covering slag in use, when wherein rare earth oxide content reached 10% left and right sides, its recrystallization temperature can rise to about 1100 ℃ by about 930 ℃; heat flow density between strand and crystallizer is better controlled, and heat transfer becomes even.The incidence of defectives such as surface longitudinal crack of slab declines to a great extent; adopting the weathering steel continuous casting billet blemish incidence of commercially available crystallizer protecting residue casting is about 20%, and adopting the weathering steel continuous casting billet blemish incidence of crystallizer protecting residue casting of the present invention is in 3%.Simultaneously the setting temperature of covering slag also rises to about 1140 ℃ by about 950 ℃, has still kept the good lubrication to strand, helps reducing the incidence of the bonding steel leakage accident of casting process.
In a word, covering slag of the present invention melts in crystallizer evenly, a little less than the reaction of rare-earth wires, lubricated good to strand, the heat transfer between crystallizer and strand evenly, suitably, thereby reduce breakout ratio and improve cc billet surface quality.
The specific 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.
The raw material that following examples adopt is as follows:
Pre-melt (Tongliang County, Chongqing insulation material factory produces, title CTR-2), its chemical composition (percentage by weight) is: 30%≤SiO 2≤ 36%, 0＜Al 2O 3≤ 6%, 0＜Fe 2O 3≤ 2%, 39%≤CaO≤45%, 0%＜MgO≤9%, 0%＜Na 2O≤4% also contains a small amount of K 2O, MnO and other micro-component;
Quartz sand, its chemical composition is: 100%＞SiO 2〉=99%;
Fluorite, its chemical composition is: 100%＞CaF 2〉=90%, 0＜SiO 2≤ 6%;
Calcined soda for industry, its chemical composition is: 100%＞Na 2CO 3〉=95%;
Magnesia, its chemical composition is: 100%＞MgO 〉=98%, 0＜Fe 2O 3≤ 1%;
In super carbon black, its chemical composition is: 100%＞C 〉=98%;
Graphite, its chemical composition is: 100%＞C＞94%, 0＜SiO 2＜5%;
Lithium carbonate, its chemical composition is: 100%＞Li 2O 〉=38%.
The raw material consumption that following examples adopt sees Table 1:
The consumption of raw material among table 1 embodiment
Raw material Consumption (kilogram)
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Pre-melt 64.5 64 64.5 64.5 65
Quartz sand 10.5 10.5 11 9.5 11.5
Fluorite 7 7 6.5 6 6
Calcined soda for industry 5 5.5 5.5 6 5
Magnesia 3.5 3.7 3.1 4 3.6
In super carbon black 2 2 2 2 2
Graphite 3 3 3 3.5 3
Lithium carbonate 4.5 4.3 4.4 4.5 3.9
Embodiment 1
Take by weighing needed raw material in ratio shown in the table 1, adopt atomizing granulating technology to make the hollow bead covering slag.The chemical composition of the covering slag that obtains (percentage by weight) is: SiO 232.7%, CaO 33.6%, Al 2O 34.1%, MgO 4.2%, Li 2O2.5%, Na 2O 7.3%, F 6.1%, TC 5.5%, Fe 2O 30.7%, all the other are K 2O 1.5%, MnO 0.9% and other micro-component, wherein CaO/SiO 2: 1.03, its physical property is: 932 ℃ of viscosity 0.18Pas, recrystallization temperatures, 955 ℃ of setting temperatures under 1121 ℃, 1300 ℃ of the hemisphere point fusion temperatures.This covering slag is used for 09CuPTiRE-A and 09CuPTiRE-B cast, experiment condition is: casting blank section 200mm * 1050mm, pulling rate 0.9m/min, water 1560 ℃ of steel temperature, spreadability and good fluidity in crystallizer, the top of the slag is active, a little less than the reaction of rare-earth wires, the top of the slag does not have lack of fusion phenomenons such as conglomeration, caking, does not produce the slag bar; Liquid slag layer thickness 11～15mm, the slag consumption is 0.65～0.70kg/t steel; The bleed-out accident does not take place; Defective incidences such as institute's 09CuPTiRE-A surface longitudinal crack of slab that waters are 1.1%, and defective incidences such as institute's 09CuPTiRE-B surface longitudinal crack of slab that waters are 0.4%.
Embodiment 2
Take by weighing required raw material in ratio shown in the table 1, adopt atomizing granulating technology to make the hollow bead covering slag.The chemical composition of the covering slag that obtains (percentage by weight) is: SiO 233.8%, CaO 33.6%, Al 2O 34.1%, MgO 4.3%, Li 2O 2.3%, Na 2O 6.8%, F 5.9%, TC 6.1%, Fe 2O 30.8%, all the other are K 2O 1.1%, MnO 0.5% and other micro-component, wherein CaO/SiO 2: 0.99.Its physical property is: 932 ℃ of viscosity 0.20Pas, recrystallization temperatures, 953 ℃ of setting temperatures under 1112 ℃, 1300 ℃ of the hemisphere point fusion temperatures.This covering slag is used for 09CuPTiRE-A and 09CuPCrNi-A cast, experiment condition is: casting blank section 200mm * 1060mm, pulling rate 0.85m/min, water 1555 ℃ of steel temperature, spreadability and good fluidity in crystallizer, the top of the slag is active, a little less than the reaction of rare-earth wires, the top of the slag does not have lack of fusion phenomenons such as conglomeration, caking, does not produce the slag bar; Liquid slag layer thickness 10～14mm, the slag consumption is 0.65～0.70kg/t steel; The bleed-out accident does not take place; Defective incidences such as institute's 09CuPTiRE-A surface longitudinal crack of slab that waters are 2.7%, and defective incidences such as institute's 09CuPCrNi-A surface longitudinal crack of slab that waters are 1.2%.
Embodiment 3
Take by weighing required raw material in ratio shown in the table 1, adopt atomizing granulating technology to make the hollow bead covering slag.The chemical composition of the covering slag that obtains (percentage by weight) is: SiO 234.3%, CaO 33.7%, Al 2O 34.5%, MgO 3.6%, Li 2O 2.3%, Na 2O 7.4%, F 6.6%, TC 5.1%, Fe 2O 30.6%, all the other are K 2O 0.8%, MnO 0.3% and other micro-component, wherein CaO/SiO 2: 0.98.Its physical property is: 913 ℃ of viscosity 0.19Pas, recrystallization temperatures, 942 ℃ of setting temperatures under 1135 ℃, 1300 ℃ of the hemisphere point fusion temperatures.This covering slag is used for 09CuPRE and 09CuPCrNi-A cast, experiment condition is: casting blank section 200mm * 1250mm, pulling rate 0.82m/min, water 1565 ℃ of steel temperature, spreadability and good fluidity in crystallizer, the top of the slag is active, a little less than the reaction of rare-earth wires, the top of the slag does not have lack of fusion phenomenons such as conglomeration, caking, does not produce the slag bar; Liquid slag layer thickness 10～14mm, the slag consumption is 0.65～0.70kg/t steel; The bleed-out accident does not take place; Defective incidences such as institute's 09CuPRE surface longitudinal crack of slab that waters are 1.9%, and defective incidences such as institute's 09CuPCrNi-A steel surface longitudinal crack of slab that waters are 1.7%.
Embodiment 4
Take by weighing required raw material in ratio shown in the table 1, adopt atomizing granulating technology to make the hollow bead covering slag.The chemical composition of the covering slag that obtains (percentage by weight) is: SiO 230.9%, CaO 32.4%, Al 2O 34.7%, MgO 5.5%, Li 2O 2.4%, Na 2O 8.1%, F 6.8%, TC 6.3%, Fe 2O 30.7%, all the other are K 2O 0.9%, MnO 0.7% and other micro-component, wherein CaO/SiO 2: 1.05.Its physical property is: 909 ℃ of viscosity 0.22Pas, recrystallization temperatures, 931 ℃ of setting temperatures under 1098 ℃, 1300 ℃ of the hemisphere point fusion temperatures.This covering slag is used for 09CuPTiRE-A and 09CuPRE cast, experiment condition is: casting blank section 200mm * 1250mm, pulling rate 0.84m/min, water 1563 ℃ of steel temperature, spreadability and good fluidity in crystallizer, the top of the slag is active, a little less than the reaction of rare-earth wires, the top of the slag does not have lack of fusion phenomenons such as conglomeration, caking, does not produce the slag bar; Liquid slag layer thickness 12～14mm, the slag consumption is 0.65～0.70kg/t steel; The bleed-out accident does not take place; Defective incidences such as institute's 09CuPTiRE-A surface longitudinal crack of slab that waters are 0.5%, and defective incidences such as institute's 09CuPRE surface longitudinal crack of slab that waters are 1.3%.
Embodiment 5
Take by weighing required raw material in ratio shown in the table 1, adopt atomizing granulating technology to make the hollow bead covering slag.The chemical composition of the covering slag that obtains (percentage by weight) is: SiO 236.2%, CaO 34.5%, Al 2O 33.2%, MgO 4.0%, Li 2O1.7%, Na 2O 6.1%, F 6.0%, TC 5.4%, Fe 2O 30.6%, all the other are K 2O 0.9%, MnO 0.5% and other micro-component, wherein CaO/SiO 2: 0.95.Its physical property is: the viscosity 0.26 under 1145 ℃, 1300 ℃ of the hemisphere point fusion temperatures
Pas, 953 ℃ of recrystallization temperatures, 972 ℃ of setting temperatures.This covering slag is used for 09CuPTiRE-A and 09CuPRE cast, experiment condition is: casting blank section 200mm * 1250mm, pulling rate 0.83m/min, water 1560 ℃ of steel temperature, spreadability and good fluidity in crystallizer, the top of the slag is active, a little less than the reaction of rare-earth wires, the top of the slag does not have lack of fusion phenomenons such as conglomeration, caking, does not produce the slag bar; Liquid slag layer thickness 10～13mm, the slag consumption is 0.65～0.70kg/t steel; The bleed-out accident does not take place; Defective incidences such as institute's 09CuPTiRE-A surface longitudinal crack of slab that waters are 1.1%, and defective incidences such as institute's 09CuPRE surface longitudinal crack of slab that waters are 1.5%.

Claims (9)

1. continuous casting crystallizer protective scoria for weathering steel, it is characterized in that: the constituent of described covering slag contains by weight percentage: SiO 230.0～37.0%, CaO 30.0～37.0%,
Al 2O 3 2.0～5.0％、MgO 3.0～6.0％、Li 2O 1.5～2.5％、Na 2O 5.5～8.5％、F 4.5～7.5％、TC 4.5～6.5％、0＜Fe 2O 3≤1.0％。
2. continuous casting crystallizer protective scoria for weathering steel as claimed in claim 1 is characterized in that: described covering slag dual alkalinity CaO/SiO 2Be 0.95～1.05.
3. continuous casting crystallizer protective scoria for weathering steel as claimed in claim 1 or 2 is characterized in that: the constituent that described covering slag contains is preferably by weight percentage: SiO 230.7～36.4%, CaO 31.8～36.1%, Al 2O 32.8～4.9%, MgO 3.3～5.7%, Li 2O 1.6～2.5%, Na 2O 5.8～8.3%, F 4.9～7.0%, TC 4.8～6.4%, 0＜Fe 2O 3≤ 1.0%.
4. continuous casting crystallizer protective scoria for weathering steel as claimed in claim 1 is characterized in that: described covering slag physicochemical property is: 900～960 ℃ of viscosity 0.17～0.27 Pas, recrystallization temperatures, 920～980 ℃ of setting temperatures under 1090～1150 ℃, 1300 ℃ of the hemisphere point fusion temperatures.
5. continuous casting crystallizer protective scoria for weathering steel as claimed in claim 1 is characterized in that: described covering slag by pre-melt, quartz sand, fluorite, calcined soda for industry, magnesia, in raw materials such as super carbon black, graphite, lithium carbonate adopt atomizing granulating technology to make.
6. continuous casting crystallizer protective scoria for weathering steel as claimed in claim 1 is characterized in that: covering slag moisture content of finished products≤0.50%, granularity＜2.0mm.
7. continuous casting crystallizer protective scoria for weathering steel as claimed in claim 6 is characterized in that: granularity 0.2～1.0mm level 〉=80% in the covering slag finished product, and less than 0.2mm level＜15%.
8. the preparation method of a continuous casting crystallizer protective scoria for weathering steel as claimed in claim 1, it is characterized in that: this method is made up of following steps:
A) chemical composition of detection raw material;
B) with pre-melt, quartz sand, fluorite, magnesia break process;
C), calculate the weight of needed raw material according to the satisfying condition of covering slag chemical composition;
D) take by weighing above-mentioned raw materials premix in the twin-screw mixing procedure machine in proportion, send into to stir in the mill and make slurry;
E) slurry is imported pans, send into mist projection granulating in the spray tower by high-pressure pump.
9. the preparation method of continuous casting crystallizer protective scoria for weathering steel as claimed in claim 8 is characterized in that: described step b) is crossed 320 mesh sieves for crossing 180 mesh sieves after pre-melt, quartz sand, the fluorite fragmentation after the magnesia fragmentation
CNB2007102017505A 2007-09-18 2007-09-18 Continuous casting crystallizer protective scoria for weathering steel and manufacturing method thereof Expired - Fee Related CN100528406C (en)

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CN108474061A (en) * 2016-01-12 2018-08-31 尤米科尔公司 Metallurgical slag rich in lithium
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CN111363972A (en) * 2018-12-25 2020-07-03 新疆八一钢铁股份有限公司 Production method of weathering resistant steel Q355NHD
CN112247088A (en) * 2020-10-31 2021-01-22 江苏沙钢集团有限公司 Silicon steel crystallizer covering slag
CN113523215A (en) * 2021-06-18 2021-10-22 首钢集团有限公司 Process for effectively controlling continuous casting bleed-out of high-manganese steel slab
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CN112247088A (en) * 2020-10-31 2021-01-22 江苏沙钢集团有限公司 Silicon steel crystallizer covering slag
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