WO2022022629A1 - Refining slag capable of obtaining cao-sio2-mgo-based low-melting-point inclusions - Google Patents
Refining slag capable of obtaining cao-sio2-mgo-based low-melting-point inclusions Download PDFInfo
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- WO2022022629A1 WO2022022629A1 PCT/CN2021/109204 CN2021109204W WO2022022629A1 WO 2022022629 A1 WO2022022629 A1 WO 2022022629A1 CN 2021109204 W CN2021109204 W CN 2021109204W WO 2022022629 A1 WO2022022629 A1 WO 2022022629A1
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- refining slag
- cao
- sio
- mgo
- inclusions
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- 238000007670 refining Methods 0.000 title claims abstract description 67
- 239000002893 slag Substances 0.000 title claims abstract description 67
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 31
- 239000010959 steel Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000007664 blowing Methods 0.000 claims description 8
- 238000010079 rubber tapping Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000003628 erosive effect Effects 0.000 abstract description 7
- 239000011819 refractory material Substances 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- 229910020413 SiO2—MgO Inorganic materials 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 238000005098 hot rolling Methods 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000002844 melting Methods 0.000 description 11
- 238000005096 rolling process Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910004261 CaF 2 Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910000639 Spring steel Inorganic materials 0.000 description 1
- RWDBMHZWXLUGIB-UHFFFAOYSA-N [C].[Mg] Chemical compound [C].[Mg] RWDBMHZWXLUGIB-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920013754 low-melting plastic Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000009865 steel metallurgy Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/36—Processes yielding slags of special composition
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- 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
Definitions
- the invention belongs to the technical field of secondary refining in the iron and steel metallurgy industry, and particularly relates to a refining slag for obtaining CaO-SiO 2 -MgO series low-melting-point inclusions.
- Cord steel is a steel wire with a diameter of 0.15 to 0.38 mm, which is mainly used to make tire meridians. Due to the extremely small diameter of the cord steel wire and the complex force in the production process, once there are large-sized non-deformable inclusions in the steel, the wire will be broken during the drawing or plying process, which will seriously affect the production efficiency and even cause product degradation or scrapping. Studies have shown that controlling the inclusions in the steel as low-melting plastic inclusions can reduce the wire breakage rate of the cord steel.
- the current refining process obtains low melting point plastic inclusions, the erosion of the ladle slag line by the low alkalinity acidic CaO-SiO 2 slag is very serious.
- the ladle age of smelting cord steel using low-basicity slag is only one third of that of ordinary refining slag, or even lower. Therefore, the refining of acid slag with low alkalinity results in the high cost of ladle refractories in the current cord steel production process.
- CaO-SiO 2 -Al 2 O 3 -MgO-based low-melting-point inclusions are easily recrystallized during cooling and solidification or long-term heating, resulting in hard Al 2 O 3 -MgO-based spinel inclusions. In order to prevent deformation and inclusions, it is easy to cause wire breakage during the processing of cord steel.
- a method for refining spring steel proposes the CaO-SiO 2 -MgO slag system, and the inclusions after refining are not studied.
- the composition and shape of the components, and the melting point of the refining slag of this component is very high, and the refining composition is not easy to be melted into slag, so additional CaF 2 needs to be added for fluxing.
- the addition of CaF 2 can reduce the melting point of the refining slag. 2
- the erosion of the ladle is very serious, which also leads to the reduction of the age of the ladle.
- CaF 2 is an environmentally unfriendly slag, and the F element it contains will pollute the environment. In many developed countries, CaF 2 is clearly prohibited in steelmaking slag. of.
- the present invention provides a refining slag for obtaining CaO-SiO 2 -MgO series low-melting-point inclusions.
- the electrode is heated to increase the temperature, and the heating temperature should be controlled between 1565 and 1585 ° C.
- the refining slag of the above components added during the tapping process is slag-forming, and the ladle is bottom-blown with argon during the entire LF treatment process.
- control the acid molten aluminum Als in molten steel to be less than or equal to 8ppm, and the dissolved oxygen [O] is 15-25ppm.
- the total treatment time of LF is 50min, wherein the time of soft blowing argon is preferably 35min.
- the present invention requires that the basicity (CaO/SiO 2 ) is in the range of 0.7-1.0 and the content of MgO is controlled to be 15-25%.
- the basicity CaO/SiO 2
- the content of MgO is controlled to be 15-25%.
- the content of Al 2 O 3 in the refining slag of the present invention is within 2%, and the cord steel is generally smelted with low titanium and low aluminum ferrosilicon and metal manganese.
- the Al content in these alloys is extremely low, so the inclusions contain Al 2 O
- the content of 3 is very low and can be ignored, avoiding the crystallization of hard and non-deformable MgO-Al 2 O 3 spinel-like inclusions during continuous casting.
- the invention produces low-melting-point inclusions that can be fully deformed, which significantly reduces the wire breakage rate of the cord steel.
- the present invention proposes a refining slag for obtaining CaO-SiO 2 -MgO series low melting point inclusions, and obtains CaO-SiO 2 -MgO series low melting point inclusions after refining At the same time, it can effectively reduce the erosion of the refining slag to the magnesium-carbon slag wire.
- the ladle age of the cord ladle can be increased by more than 2 times, and the oxide inclusions in the wire rod can be fully and uniformly deformed along the rolling direction.
- the width is less than 2 microns, which further reduces the wire breakage rate of the cord steel and greatly reduces the cost of the cord steel ladle.
- Fig. 1 is the morphology along the rolling direction of CaO-SiO 2 -MgO inclusions in the wire rod obtained in Example 1;
- Fig. 2 is the morphology of CaO-SiO 2 -MgO inclusions in the wire rod obtained in Example 2 along the rolling direction;
- Fig. 3 is the morphology along the rolling direction of CaO-SiO 2 -MgO inclusions in the wire rod obtained in Example 3;
- Fig. 4 is the morphology along the rolling direction of CaO-SiO 2 -MgO inclusions in the wire rod obtained in Example 4;
- Fig. 5 is the lateral width size distribution of inclusions in Examples 1-4;
- Fig. 6 is the projection of inclusion composition in the wire rod obtained in Example 1-4;
- Figure 7 shows the composition and morphology of the inclusions obtained in Comparative Example 1;
- Figure 8 shows the composition and morphology of the inclusions obtained in Comparative Example 2.
- test steel grade is LX82A, and its chemical composition is shown in Table 1.
- the test process can adopt the production process of cord steel commonly used in this field, namely "converter steelmaking-LF refining-continuous casting-wire rod rolling" , the test flow adopted in the following examples is specifically as follows: (other undisclosed conditions are all LX82A conventional smelting conditions)
- 1Converter process The high-draw carbon process is used at the end of the converter, and metal manganese, low-titanium, low-aluminum ferrosilicon and recarburizers are added in the converter tapping process. After the tapping is completed, metal manganese, low titanium and low aluminum ferrosilicon and the refining slag designed by the present invention are added.
- the addition amount of metal manganese and low titanium and low aluminum ferrosilicon is based on the principle that the content of Mn and Si in the steel reaches or is close to the requirements of the finished product. , the amount of refining slag added is 8 ⁇ 10kg / ton of steel.
- 2LF refining process the electrode is heated to increase temperature, and the heating temperature should be controlled between 1565 and 1585 ° C (preferably 1570 ° C), and the refining slag (any one of 1#-7#) added during the tapping process is slag.
- the ladle is agitated by bottom blowing argon, and the composition of molten steel is fine-tuned to make the composition of molten steel meet the requirements of the finished product.
- the total processing time of LF is ⁇ 45min (preferably 50min), of which the time of soft argon blowing is ⁇ 25min (preferably 35min). .
- the acid-dissolved aluminum Als in the molten steel is controlled to be ⁇ 8ppm, and the dissolved oxygen [O] is 15-25ppm.
- 160mm ⁇ 160mm billet is obtained by continuous casting, the billet is heated to 1050-1100°C, kept for 2 hours, and rolled into a cord steel wire rod with a diameter of 5.5mm.
- the refining slag added to the ladle in this example is the 1# refining slag in Table 2.
- the refining slag added to the ladle in this example is the 2# refining slag in Table 2.
- the refining slag added to the ladle in this example is the 3# refining slag in Table 2.
- the refining slag added to the ladle in this example is the 4# refining slag in Table 2.
- the refining slag added to the ladle in this example is the 5# refining slag in Table 3.
- the basicity of the refining slag is higher than 1.0. It can be seen from Figure 7 that magnesium-aluminum spinel is precipitated in the inclusions in the production wire rod, and the inclusions are not sufficiently deformed and are lumpy, which increases the risk of wire breakage.
- the refining slag added to the ladle in this example is the 6# refining slag in Table 3.
- the content of Al 2 O 3 in the inclusions is higher than 3%. It can be seen from Figure 8 that the inclusions in the wire rods are precipitated by magnesia-aluminum spinel, and the inclusions are not sufficiently deformed and are lumpy, which increases the risk of wire breakage.
- the refining slag added to the ladle is the 7# refining slag in Table 3, smelted until the life of the ladle ends, and the ladle age of the ladle is counted.
- MgO content is less than 15%, a large amount of MgO in the refractory material will dissolve into the refining slag, and the erosion of the refractory material is very serious, reducing the age of the package.
- FIG. 1 to 4 show the morphology of oxide inclusions in the wire rods obtained in Examples 1 to 4 along the rolling direction, respectively. It can be seen that the oxides in the wire rods obtained by using the refining slag of the present invention are sufficiently deformed along the rolling direction. Uniform, the lateral width is less than 2 microns, and most of the inclusion sizes are less than 1.2 microns wide, as shown in Figure 5.
- FIG. 6 is a projection of the composition of the inclusions in Examples 1-4.
- the inclusions are CaO-SiO 2 -MgO, which is in the low melting point region of the CaO-SiO 2 -MgO system.
- Figures 7 and 8 show the composition and morphology of the inclusions obtained in Comparative Example 1 and Comparative Example 2, respectively. Magnesium-aluminum spinel is precipitated in the inclusions, and the inclusions are not sufficiently deformed and are lumpy.
- the ladle age ranges from 23 to 29 heats (average 25 heats), and the refining slag of the present invention is used.
- the package age can be increased to 71-83 furnaces (average 76 furnaces).
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- Engineering & Computer Science (AREA)
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- Treatment Of Steel In Its Molten State (AREA)
Abstract
Provided is a refining slag capable of obtaining CaO-SiO2-MgO-based low-melting-point inclusions. The refining slag can be used for the refining of cord steel. The present invention belongs to the field of secondary refining in the steel and metallurgical industry and is characterized in that the composition of the refining slag is rationally designed. The refining slag has the following components in mass percentages: MgO = 15-25% and Al2O3 < 3%, with the balance being CaO and SiO2, wherein the mass ratio of CaO to SiO2 is 0.7:1.0. Industrial applications have shown that the refining slag designed by the present invention can obtain low-melting-point CaO-SiO2-MgO-based inclusions. Such inclusions are deformed uniformly and sufficiently during hot rolling, and the width of the inclusions in the final wire rod can be controlled to be 2 microns or less. In addition, the erosion of the refining slag into a ladle refractory material can be reduced, and the ladle age can be increased by twofold or more.
Description
本发明属于钢铁冶金行业二次精炼技术领域，特别涉及一种获得CaO-SiO
2-MgO系低熔点夹杂物的精炼渣。
The invention belongs to the technical field of secondary refining in the iron and steel metallurgy industry, and particularly relates to a refining slag for obtaining CaO-SiO 2 -MgO series low-melting-point inclusions.
帘线钢是直径0.15～0.38mm的钢丝，主要用于制作轮胎子午线。由于帘线钢丝线径极细且制作过程受力复杂，钢中一旦存在大尺寸不变形夹杂，钢丝在拉拔或者合股过程中就会发生断线，严重影响生产效率甚至造成产品降级或报废。研究表明，将钢中夹杂物控制为低熔点塑性夹杂可降低帘线钢的断丝率。Cord steel is a steel wire with a diameter of 0.15 to 0.38 mm, which is mainly used to make tire meridians. Due to the extremely small diameter of the cord steel wire and the complex force in the production process, once there are large-sized non-deformable inclusions in the steel, the wire will be broken during the drawing or plying process, which will seriously affect the production efficiency and even cause product degradation or scrapping. Studies have shown that controlling the inclusions in the steel as low-melting plastic inclusions can reduce the wire breakage rate of the cord steel.
为获得低熔点塑性夹杂物，目前行业通用的控制手段是利用低碱度酸性CaO-SiO
2渣系(CaO/SiO
2＝0.8～1.2，Al
2O
3<10％，MgO<10％)精炼，通过控制渣钢反应将夹杂物控制在CaO-SiO
2-Al
2O
3-MgO低熔点区。目前的精炼工艺虽然获得低熔点塑性夹杂，但是低碱度酸性CaO-SiO
2渣对钢包渣线的侵蚀十分严重。使用低碱度渣冶炼帘线钢的钢包包龄仅是采用普通精炼渣包龄的三分之一，甚至更低。因此，低碱度酸性渣精炼造成目前帘线钢生产过程钢包耐材成本高昂。此外，CaO-SiO
2-Al
2O
3-MgO系低熔点夹杂在冷却凝固或长时间加热过程极易二次结晶，生成硬质的Al
2O
3-MgO系尖晶石夹杂，此类夹杂为不变形夹杂，极易引起帘线钢加工过程的断丝。也有少数方案中涉及CaO-SiO
2-MgO渣系的应用，如：“CN201610585085.3一种弹簧钢的精炼方法”中就提出了CaO-SiO
2-MgO渣系，其中未研究精炼后的夹杂成分组成和形态，并且该组分的精炼渣的熔点很高，精炼构成不易熔化成渣，所以还需额外加入CaF
2助熔，CaF
2的加入可以起到降低精炼渣熔点的作用，但CaF
2对钢包的侵蚀十分严重，同样导致钢包包龄 降低，另外CaF
2属于环境不友好的渣料，所含F元素会污染环境，在很多发达国家CaF
2在炼钢渣料中是明确禁止使用的。
In order to obtain low melting point plastic inclusions, the current common control method in the industry is to use low basicity acidic CaO-SiO 2 slag system (CaO/SiO 2 =0.8～1.2, Al 2 O 3 <10%, MgO<10%) refining , the inclusions are controlled in the low melting point region of CaO-SiO 2 -Al 2 O 3 -MgO by controlling the slag-steel reaction. Although the current refining process obtains low melting point plastic inclusions, the erosion of the ladle slag line by the low alkalinity acidic CaO-SiO 2 slag is very serious. The ladle age of smelting cord steel using low-basicity slag is only one third of that of ordinary refining slag, or even lower. Therefore, the refining of acid slag with low alkalinity results in the high cost of ladle refractories in the current cord steel production process. In addition, CaO-SiO 2 -Al 2 O 3 -MgO-based low-melting-point inclusions are easily recrystallized during cooling and solidification or long-term heating, resulting in hard Al 2 O 3 -MgO-based spinel inclusions. In order to prevent deformation and inclusions, it is easy to cause wire breakage during the processing of cord steel. There are also a few schemes involving the application of the CaO-SiO 2 -MgO slag system, such as: "CN201610585085.3 A method for refining spring steel" proposes the CaO-SiO 2 -MgO slag system, and the inclusions after refining are not studied. The composition and shape of the components, and the melting point of the refining slag of this component is very high, and the refining composition is not easy to be melted into slag, so additional CaF 2 needs to be added for fluxing. The addition of CaF 2 can reduce the melting point of the refining slag. 2 The erosion of the ladle is very serious, which also leads to the reduction of the age of the ladle. In addition, CaF 2 is an environmentally unfriendly slag, and the F element it contains will pollute the environment. In many developed countries, CaF 2 is clearly prohibited in steelmaking slag. of.
因此，在环境友好的前提下，如何设计一种新型精炼渣，不含CaF
2助熔，在提高钢包包龄的同时又能获得变形性能优异的低熔点夹杂是本发明所要解决的技术问题。
Therefore, under the premise of environmental friendliness, how to design a new type of refining slag, which does not contain CaF 2 for fluxing, can obtain low-melting inclusions with excellent deformability while increasing the ladle age is the technical problem to be solved by the present invention.
发明内容SUMMARY OF THE INVENTION
本发明为解决上述技术问题，提供了一种获得CaO-SiO
2-MgO系低熔点夹杂物的精炼渣。
In order to solve the above technical problems, the present invention provides a refining slag for obtaining CaO-SiO 2 -MgO series low-melting-point inclusions.
为实现上述目的，本发明所采用的技术方案如下：For achieving the above object, the technical scheme adopted in the present invention is as follows:
一种获得CaO-SiO
2-MgO系低熔点夹杂物的精炼渣，所述精炼渣中各组份的质量百分比为MgO＝15～25％，Al
2O
3<3％，其余为CaO和SiO
2，其中CaO与SiO
2的质量比为0.7～1.0。
A refining slag for obtaining CaO-SiO 2 -MgO series low-melting-point inclusions, the mass percentage of each component in the refining slag is MgO=15-25%, Al 2 O 3 <3%, and the rest are CaO and SiO 2 , wherein the mass ratio of CaO to SiO 2 is 0.7 to 1.0.
在LF精炼工序中：电极加热升温，加热温度要控制在1565～1585℃之间，对出钢过程中加入的上述组分的精炼渣进行造渣，在LF整个处理过程钢包进行底吹氩气搅拌，并对钢液成分进行微调，使钢液成分满足成品要求，LF总处理时间≥45min，软吹氩时间≥25min。In the LF refining process: the electrode is heated to increase the temperature, and the heating temperature should be controlled between 1565 and 1585 ° C. The refining slag of the above components added during the tapping process is slag-forming, and the ladle is bottom-blown with argon during the entire LF treatment process. Stir, and fine-tune the composition of the molten steel, so that the composition of the molten steel meets the requirements of the finished product, the total processing time of LF is ≥45min, and the time of soft argon blowing is ≥25min.
进一步，LF软吹氩完毕后，控制钢水中酸熔铝Als≤8ppm，溶解氧[O]在15～25ppm。Further, after the LF soft blowing of argon is completed, control the acid molten aluminum Als in molten steel to be less than or equal to 8ppm, and the dissolved oxygen [O] is 15-25ppm.
作为优选，LF总处理时间为50min，其中软吹氩时间优选为35min。Preferably, the total treatment time of LF is 50min, wherein the time of soft blowing argon is preferably 35min.
本发明要求碱度(CaO/SiO
2)在0.7～1.0范围并协同控制MgO的含量在15～25％，共同限定后的精炼渣在1565～1585℃精炼温度下精炼时间≥45min，最终才能在降低钢包侵蚀的同时获得变形更充分的低熔点夹杂，则无需再加入其它助熔剂(如CaF
2)化渣助熔来降低熔点，不仅降低成本，环境友好，避免助 熔剂对钢包的侵蚀。
The present invention requires that the basicity (CaO/SiO 2 ) is in the range of 0.7-1.0 and the content of MgO is controlled to be 15-25%. To reduce the erosion of the ladle and obtain low-melting inclusions with more sufficient deformation, there is no need to add other fluxes (such as CaF 2 ) to reduce the melting point by slag fluxing, which not only reduces the cost, but also is environmentally friendly and avoids the erosion of the ladle by the flux.
本发明的精炼渣中Al
2O
3含量在2％以内，且帘线钢一般都使用低钛低铝硅铁和金属锰冶炼，这些合金中的Al含量极低，所以夹杂物中Al
2O
3含量非常低，可忽略不计，避免在连铸时结晶生产硬质不变形的MgO-Al
2O
3尖晶石类夹杂。本发明生成的均是能充分变形的低熔点夹杂，显著降低帘线钢的断丝率。
The content of Al 2 O 3 in the refining slag of the present invention is within 2%, and the cord steel is generally smelted with low titanium and low aluminum ferrosilicon and metal manganese. The Al content in these alloys is extremely low, so the inclusions contain Al 2 O The content of 3 is very low and can be ignored, avoiding the crystallization of hard and non-deformable MgO-Al 2 O 3 spinel-like inclusions during continuous casting. The invention produces low-melting-point inclusions that can be fully deformed, which significantly reduces the wire breakage rate of the cord steel.
与现有技术相比，本发明的有益效果为：本发明提出的一种获得CaO-SiO
2-MgO系低熔点夹杂物的精炼渣，精炼后获得CaO-SiO
2-MgO系低熔点夹杂物的同时有效降低精炼渣对镁碳质渣线的侵蚀，与现有工艺相比，可将帘线钢钢包包龄提高2倍以上，盘条中氧化物夹杂沿轧制方向变形充分且均匀，宽度在2微米以下，从而起到进一步降低帘线钢的断丝率的作用，大大降低帘线钢钢包成本。
Compared with the prior art, the beneficial effects of the present invention are as follows: the present invention proposes a refining slag for obtaining CaO-SiO 2 -MgO series low melting point inclusions, and obtains CaO-SiO 2 -MgO series low melting point inclusions after refining At the same time, it can effectively reduce the erosion of the refining slag to the magnesium-carbon slag wire. Compared with the existing process, the ladle age of the cord ladle can be increased by more than 2 times, and the oxide inclusions in the wire rod can be fully and uniformly deformed along the rolling direction. The width is less than 2 microns, which further reduces the wire breakage rate of the cord steel and greatly reduces the cost of the cord steel ladle.
图1为实施例1所得盘条中CaO-SiO
2-MgO夹杂沿轧制方向形貌；
Fig. 1 is the morphology along the rolling direction of CaO-SiO 2 -MgO inclusions in the wire rod obtained in Example 1;
图2为实施例2所得盘条中CaO-SiO
2-MgO夹杂沿轧制方向形貌；
Fig. 2 is the morphology of CaO-SiO 2 -MgO inclusions in the wire rod obtained in Example 2 along the rolling direction;
图3为实施例3所得盘条中CaO-SiO
2-MgO夹杂沿轧制方向形貌；
Fig. 3 is the morphology along the rolling direction of CaO-SiO 2 -MgO inclusions in the wire rod obtained in Example 3;
图4为实施例4所得盘条中CaO-SiO
2-MgO夹杂沿轧制方向形貌；
Fig. 4 is the morphology along the rolling direction of CaO-SiO 2 -MgO inclusions in the wire rod obtained in Example 4;
图5为实施例1-4夹杂物横向宽度尺寸分布；Fig. 5 is the lateral width size distribution of inclusions in Examples 1-4;
图6为实施例1-4所得盘条中夹杂物成分投影；Fig. 6 is the projection of inclusion composition in the wire rod obtained in Example 1-4;
图7为对比例1所得夹杂物成分和形貌；Figure 7 shows the composition and morphology of the inclusions obtained in Comparative Example 1;
图8为对比例2所得夹杂物成分和形貌。Figure 8 shows the composition and morphology of the inclusions obtained in Comparative Example 2.
下面结合附图及具体实施例对本发明作进一步的详细说明：The present invention will be described in further detail below in conjunction with the accompanying drawings and specific embodiments:
以下实施例中，试验钢种为LX82A，其化学成分见表1，试验流程可采用 本领域中常用的帘线钢生产工序，即“转炉炼钢—LF精炼—连续浇铸—盘条轧制”，以下实施例采用的试验流程具体如下所述：(其它未公开的条件均是LX82A常规冶炼条件)In the following examples, the test steel grade is LX82A, and its chemical composition is shown in Table 1. The test process can adopt the production process of cord steel commonly used in this field, namely "converter steelmaking-LF refining-continuous casting-wire rod rolling" , the test flow adopted in the following examples is specifically as follows: (other undisclosed conditions are all LX82A conventional smelting conditions)
①转炉工序：转炉终点采用高拉碳工艺，转炉出钢过程加入金属锰、低钛低铝硅铁以及增碳剂。出钢完成后加入金属锰、低钛低铝硅铁和本发明所设计的精炼渣，金属锰和低钛低铝硅铁的加入量以使钢中Mn和Si含量达到或接近成品要求为原则，精炼渣的加入量为8～10kg/吨钢。①Converter process: The high-draw carbon process is used at the end of the converter, and metal manganese, low-titanium, low-aluminum ferrosilicon and recarburizers are added in the converter tapping process. After the tapping is completed, metal manganese, low titanium and low aluminum ferrosilicon and the refining slag designed by the present invention are added. The addition amount of metal manganese and low titanium and low aluminum ferrosilicon is based on the principle that the content of Mn and Si in the steel reaches or is close to the requirements of the finished product. , the amount of refining slag added is 8 ~ 10kg / ton of steel.
②LF精炼工序：电极加热升温，加热温度要控制在1565～1585℃之间(优选1570℃)，对出钢过程中加入的精炼渣(1#-7#中任一种)进行造渣，在LF整个处理过程钢包进行底吹氩气搅拌，并对钢液成分进行微调，使钢液成分满足成品要求，LF总处理时间≥45min(优选50min)，其中软吹氩时间≥25min(优选35min)。LF软吹氩完毕后，控制钢水中酸溶铝Als≤8ppm，溶解氧[O]在15～25ppm。②LF refining process: the electrode is heated to increase temperature, and the heating temperature should be controlled between 1565 and 1585 ° C (preferably 1570 ° C), and the refining slag (any one of 1#-7#) added during the tapping process is slag. In the whole process of LF treatment, the ladle is agitated by bottom blowing argon, and the composition of molten steel is fine-tuned to make the composition of molten steel meet the requirements of the finished product. The total processing time of LF is ≥45min (preferably 50min), of which the time of soft argon blowing is ≥25min (preferably 35min). . After the LF soft blowing of argon is completed, the acid-dissolved aluminum Als in the molten steel is controlled to be ≤8ppm, and the dissolved oxygen [O] is 15-25ppm.
③连续浇铸及盘条轧制工序：经连续浇铸获得160mm×160mm小方坯，小方坯加热至1050-1100℃，保温2小时，轧制成直径5.5mm的帘线钢盘条。③Continuous casting and wire rod rolling process: 160mm×160mm billet is obtained by continuous casting, the billet is heated to 1050-1100℃, kept for 2 hours, and rolled into a cord steel wire rod with a diameter of 5.5mm.
实施例1：Example 1:
本实施例中向钢包中加入的精炼渣为表2中的1#精炼渣。The refining slag added to the ladle in this example is the 1# refining slag in Table 2.
实施例2：Example 2:
本实施例中向钢包中加入的精炼渣为表2中的2#精炼渣。The refining slag added to the ladle in this example is the 2# refining slag in Table 2.
实施例3：Example 3:
本实施例中向钢包中加入的精炼渣为表2中的3#精炼渣。The refining slag added to the ladle in this example is the 3# refining slag in Table 2.
实施例4：Example 4:
本实施例中向钢包中加入的精炼渣为表2中的4#精炼渣。The refining slag added to the ladle in this example is the 4# refining slag in Table 2.
对比例1Comparative Example 1
本实施例中向钢包中加入的精炼渣为表3中的5#精炼渣。The refining slag added to the ladle in this example is the 5# refining slag in Table 3.
精炼渣碱度高于1.0，从图7可知，生产盘条中的夹杂物中有镁铝尖晶石析出，夹杂物变形不充分，呈块状，增加断丝风险。The basicity of the refining slag is higher than 1.0. It can be seen from Figure 7 that magnesium-aluminum spinel is precipitated in the inclusions in the production wire rod, and the inclusions are not sufficiently deformed and are lumpy, which increases the risk of wire breakage.
对比例2Comparative Example 2
本实施例中向钢包中加入的精炼渣为表3中的6#精炼渣。The refining slag added to the ladle in this example is the 6# refining slag in Table 3.
夹杂物中的Al
2O
3含量高于3％，从图8可知，盘条中的夹杂物有镁铝尖晶石析出，夹杂物变形不充分，呈块状，增加断丝风险。
The content of Al 2 O 3 in the inclusions is higher than 3%. It can be seen from Figure 8 that the inclusions in the wire rods are precipitated by magnesia-aluminum spinel, and the inclusions are not sufficiently deformed and are lumpy, which increases the risk of wire breakage.
对比例3Comparative Example 3
本实施例中向钢包中加入的精炼渣为表3中的7#精炼渣，冶炼至钢包寿命结束，统计钢包包龄。In this embodiment, the refining slag added to the ladle is the 7# refining slag in Table 3, smelted until the life of the ladle ends, and the ladle age of the ladle is counted.
MgO含量低于15％，耐材中的MgO会大量溶解到精炼渣中，耐材的侵蚀很严重，降低包龄。When the MgO content is less than 15%, a large amount of MgO in the refractory material will dissolve into the refining slag, and the erosion of the refractory material is very serious, reducing the age of the package.
分别取上述实施例所得盘条，使用扫描电镜检验氧化物夹杂沿轧制方向的形态。见图1至图4，分别为实施例1至4所得盘条中氧化物夹杂沿轧制方向形貌，可以看出使用本发明的精炼渣所得盘条中氧化物沿轧制方向变形充分且均匀，横向宽度在2微米以下，大部分的夹杂物尺寸宽度在1.2微米以下，如图5所示。The wire rods obtained in the above examples were respectively taken, and the morphology of oxide inclusions along the rolling direction was examined by scanning electron microscope. Figures 1 to 4 show the morphology of oxide inclusions in the wire rods obtained in Examples 1 to 4 along the rolling direction, respectively. It can be seen that the oxides in the wire rods obtained by using the refining slag of the present invention are sufficiently deformed along the rolling direction. Uniform, the lateral width is less than 2 microns, and most of the inclusion sizes are less than 1.2 microns wide, as shown in Figure 5.
图6为实施例1-4夹杂的成分投影，夹杂物成分为CaO-SiO
2-MgO，处于CaO-SiO
2-MgO系低熔点区。
FIG. 6 is a projection of the composition of the inclusions in Examples 1-4. The inclusions are CaO-SiO 2 -MgO, which is in the low melting point region of the CaO-SiO 2 -MgO system.
图7和8分别为对比例1和对比例2所得夹杂物成分和形貌，夹杂物中有镁铝尖晶石析出，夹杂物变形不充分，呈块状。Figures 7 and 8 show the composition and morphology of the inclusions obtained in Comparative Example 1 and Comparative Example 2, respectively. Magnesium-aluminum spinel is precipitated in the inclusions, and the inclusions are not sufficiently deformed and are lumpy.
此外，长期生产实践表明，采用对比例3所用的精炼渣(代表目前帘线钢的常规精炼渣)钢包的包龄范围在23～29炉不等(平均25炉)，采用本发明的精 炼渣长期生产后可将包龄提高至71～83炉(平均76炉)。In addition, long-term production practice shows that using the refining slag used in Comparative Example 3 (representing the conventional refining slag of current cord steel), the ladle age ranges from 23 to 29 heats (average 25 heats), and the refining slag of the present invention is used. After long-term production, the package age can be increased to 71-83 furnaces (average 76 furnaces).
表1试验钢种LX82A成分，质量百分比Table 1 Test steel grade LX82A composition, mass percentage
| CC | SiSi | MnMn | PP | SS | AlsAls |
| 0.830.83 | 0.200.20 | 0.490.49 | <0.01<0.01 | <0.009<0.009 | <0.0008<0.0008 |
上述实施例中1#、2#、3#、4#精炼渣分别按照表2中的原料比例配制并混合均匀。In the above example, 1#, 2#, 3#, and 4# refining slag were prepared according to the raw material ratios in Table 2 and mixed uniformly.
表2实施例所用精炼渣成分，质量百分比Table 2 embodiment used refining slag composition, mass percent
| 组号Group No | CaO/％CaO/% | SiO 2/％ SiO 2 /% | MgO/％MgO/% | Al 2O 3/％ Al 2 O 3 /% | 碱度Alkalinity |
| 1#1# | 34.134.1 | 48.648.6 | 1515 | 2.32.3 | 0.70.7 |
| 2#2# | 36.236.2 | 45.345.3 | 1818 | 0.50.5 | 0.80.8 |
| 3#3# | 36.936.9 | 40.940.9 | 21twenty one | 1.21.2 | 0.90.9 |
| 4#4# | 36.736.7 | 36.736.7 | 2525 | 1.71.7 | 1.01.0 |
表3对比例所使用的精炼渣成分，质量百分比Table 3 Refining slag composition used in the comparative example, mass percentage
| 组号Group No | CaO/％CaO/% | SiO 2/％ SiO 2 /% | MgO/％MgO/% | Al 2O 3/％ Al 2 O 3 /% | 碱度Alkalinity |
| 5#5# | 43.643.6 | 36.336.3 | 1818 | 2.12.1 | 1.21.2 |
| 6#6# | 30.930.9 | 38.738.7 | 20.320.3 | 10.110.1 | 0.80.8 |
| 7#7# | 4545 | 49.449.4 | 3.33.3 | 2.32.3 | 0.90.9 |
最后所应说明的是，以上具体实施方式仅用以说明本发明的技术方案而非限制，尽管参照实例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，其均应涵盖在本发明的权利要求范围当中。Finally, it should be noted that the above specific embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to examples, those of ordinary skill in the art should understand that the technical solutions of the present invention can be Modifications or equivalent substitutions without departing from the spirit and scope of the technical solutions of the present invention should be included in the scope of the claims of the present invention.
Claims (4)
- 一种获得CaO-SiO 2-MgO系低熔点夹杂物的精炼渣，其特征在于：所述精炼渣中各组份的质量百分比为MgO＝15～25％，Al 2O 3<3％，其余为CaO和SiO 2。 A refining slag for obtaining CaO-SiO 2 -MgO series low-melting-point inclusions, characterized in that: the mass percentage of each component in the refining slag is MgO=15-25%, Al 2 O 3 <3%, and the rest For CaO and SiO 2 .
- 如权利要求1所述的获得CaO-SiO 2-MgO系低熔点夹杂物的精炼渣，其特征在于：所述精炼渣中CaO与SiO 2的质量比为0.7～1.0。 The refining slag for obtaining CaO-SiO 2 -MgO-based low-melting-point inclusions according to claim 1, wherein the mass ratio of CaO to SiO 2 in the refining slag is 0.7-1.0.
- 如权利要求1或2所述的获得CaO-SiO 2-MgO系低熔点夹杂物的精炼渣，其特征在于：精炼渣在LF精炼工序中的应用为： The refining slag for obtaining CaO-SiO 2 -MgO series low-melting-point inclusions as claimed in claim 1 or 2, wherein the application of the refining slag in the LF refining process is:LF精炼工序中：电极加热升温，对出钢过程中加入精炼渣进行造渣，在LF整个处理过程钢包进行底吹氩气搅拌，并对钢液成分进行微调，使钢液成分满足成品要求，LF总处理时间≥45min，软吹氩时间≥25min，获得CaO-SiO 2-MgO系低熔点夹杂物。 In the LF refining process: the electrode is heated and heated up, the refining slag is added during the tapping process for slag formation, the ladle is agitated by bottom blowing argon during the entire LF treatment process, and the composition of the molten steel is fine-tuned so that the composition of the molten steel meets the requirements of the finished product. The total treatment time of LF is ≥45min, and the time of soft blowing of argon is ≥25min to obtain CaO-SiO 2 -MgO series low-melting-point inclusions.
- 如权利要求3所述的获得CaO-SiO 2-MgO系低熔点夹杂物的精炼渣，其特征在于：LF电极加热温度控制在1565～1585℃之间。 The refining slag for obtaining CaO-SiO 2 -MgO series low-melting-point inclusions according to claim 3, characterized in that the heating temperature of the LF electrode is controlled between 1565-1585°C.
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| CN109439845A (en) * | 2018-12-26 | 2019-03-08 | 武汉如星科技有限公司 | A kind of cord steel slug type calcium magnesium silicate refining slag and preparation method thereof |
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2020
- 2020-07-30 CN CN202010752034.1A patent/CN111926141B/en active Active
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2021
- 2021-07-29 KR KR1020237004179A patent/KR20230042588A/en not_active Application Discontinuation
- 2021-07-29 WO PCT/CN2021/109204 patent/WO2022022629A1/en active Application Filing
- 2021-07-29 JP JP2023504765A patent/JP2023535587A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108004374A (en) * | 2017-11-27 | 2018-05-08 | 邢台钢铁有限责任公司 | A kind of method realized oxide in cord steel and be mingled with low Young's modulus |
| CN111926141A (en) * | 2020-07-30 | 2020-11-13 | 中天钢铁集团有限公司 | Obtaining CaO-SiO2Refining slag of-MgO series low melting point inclusion |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114592105A (en) * | 2022-03-17 | 2022-06-07 | 广东韶钢松山股份有限公司 | Control method of deformed steel bar acid-soluble aluminum |
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| CN111926141A (en) | 2020-11-13 |
| JP2023535587A (en) | 2023-08-18 |
| KR20230042588A (en) | 2023-03-28 |
| CN111926141B (en) | 2024-03-26 |
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