WO2023274223A1 - 一种含钛超低碳钢的制备方法 - Google Patents

一种含钛超低碳钢的制备方法 Download PDF

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WO2023274223A1
WO2023274223A1 PCT/CN2022/101860 CN2022101860W WO2023274223A1 WO 2023274223 A1 WO2023274223 A1 WO 2023274223A1 CN 2022101860 W CN2022101860 W CN 2022101860W WO 2023274223 A1 WO2023274223 A1 WO 2023274223A1
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titanium
steel
low carbon
containing ultra
molten steel
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PCT/CN2022/101860
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English (en)
French (fr)
Chinese (zh)
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胡汉涛
吴雄
陈兆平
马志刚
张志强
职建军
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宝山钢铁股份有限公司
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Priority to DE112022003281.2T priority Critical patent/DE112022003281T5/de
Publication of WO2023274223A1 publication Critical patent/WO2023274223A1/zh

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    • 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
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/10—Handling in a vacuum
    • 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
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • 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
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0006—Adding metallic additives
    • 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
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/06—Deoxidising, e.g. killing
    • 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
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/068—Decarburising
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • 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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • 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
    • 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
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium

Definitions

  • the invention belongs to the field of metallurgical steelmaking technology, and in particular relates to a preparation method of titanium-containing ultra-low carbon steel.
  • Adding rare earth to titanium-containing ultra-low carbon steel greatly increases the frequency of nozzle nodulation during continuous casting. At this time, even if the total oxygen in the steel can be controlled to be lower than 18ppm or even lower, corresponding to the extremely low level of the total amount of inclusions in the steel, nozzle nodulation still occurs frequently.
  • Al deoxidation products Al 2 O 3
  • REM rare earth metals
  • the publication number CN1218839A emphasizes that after the decarburization of molten steel is completed, Ti is used for deoxidation, alloying, and CaSi alloy or CaSi-REM alloy is added to control the final oxide inclusion composition to be Ti 2 O 3 -CaO or REM oxide-Al 2 O 3 Composite inclusions, containing a small amount of SiO 2 or MnO, wherein the mass percentage of CaO+REM oxides is in the interval [5, 50], so as to obtain a steel plate with improved surface corrosion rate; the theoretical basis of this technology: residual oxide-based inclusions in steel In a specific composition range, the nozzle will not be blocked, and the inclusions can be finely dispersed (proposed by the inventor), so as to manufacture a steel plate with good surface properties; the comparative patent emphasizes the technological effect of its invention, which is due to the controlled addition of deoxidizing Ti content (Ti/Al ratio), the amount of Ca or REM added, so that the composition of the final inclusion is an oxide containing Ti, Ca/REM
  • the object of the present invention is to provide a preparation method of titanium-containing ultra-low carbon steel, by modifying the aluminum deoxidized substance Al 2 O 3 in the steel with rare earth, suppressing its harm and controlling the refining process at the same time
  • the oxygen content and the purity of rare earth metals in molten steel eliminate the influence of rare earth addition on continuous casting and pouring, so that rare earth treated titanium-containing ultra-low carbon steel can be pouring in a straight line, thereby effectively improving the performance of deoxidized inclusions in steel and solving the problem of molten steel It can reduce the incidence of cold rolling defects caused by Al 2 O 3 and improve the product quality of titanium-containing ultra-low carbon steel.
  • the present invention adopts the following technical solutions:
  • the invention provides a preparation method of titanium-containing ultra-low carbon steel, which includes molten iron pretreatment, primary smelting in a converter, vacuum refining, continuous casting, hot rolling, pickling and cold rolling;
  • the free oxygen content in the molten steel is 100-350ppm
  • the circulation time of the molten steel is ⁇ 3min
  • the steel Liquid circulation time ⁇ 2min, the final oxide Re 2 O 3 ⁇ Al 2 O 3 is formed in the molten steel, and the vacuum refining is completed.
  • the rare earth is Ce or La
  • REM is the mass of rare earth added
  • the unit is kg
  • T.O is the total oxygen in the steel
  • the unit is ppm;
  • the content of impurities other than rare earth elements in the rare earth is less than 0.1wt%, wherein the total oxygen T.O is less than 100ppm, and the N content is less than or equal to 30ppm.
  • the oxide Re 2 O 3 ⁇ Al 2 O 3 in the molten steel is Ce 2 O 3 ⁇ Al 2 O 3 or La2O 3 ⁇ Al 2 O 3 .
  • the circulation time of the molten steel is 3-10 min.
  • the circulating time of the molten steel is 2-10 minutes.
  • the vacuum refining device used in the vacuum refining process is a RH vacuum circulation degassing refining furnace (RH furnace) or a vacuum decarburization furnace (VD furnace) or a vacuum oxygen blowing decarburization furnace (VOD furnace).
  • RH furnace RH vacuum circulation degassing refining furnace
  • VD furnace vacuum decarburization furnace
  • VOD furnace vacuum oxygen blowing decarburization furnace
  • Adopt KR desulfurization after desulfurization, remove 70% ⁇ 80%, such as 3/4 of the top slag of molten iron;
  • the S content in the molten iron after desulfurization treatment is ⁇ 20ppm.
  • the free oxygen content in the molten steel is ⁇ 600ppm;
  • ultra-low carbon steel means that the mass percentage of finished carbon in steel is ⁇ 0.005%.
  • the titanium-containing ultra-low carbon steel comprises the following components by mass percentage: C ⁇ 0.005%, Si ⁇ 0.05%, Mn: 0.05-0.3%, Al: 0.04-0.15%, Ti: 0.04-0.1% , P ⁇ 0.05%, S ⁇ 0.02%, N ⁇ 0.003%, the balance is Fe and unavoidable impurities, and the content of Al is greater than that of Ti.
  • the titanium-containing ultra-low carbon steel comprises the following components by mass percentage: C ⁇ 0.0018%, Si ⁇ 0.03%, Mn: 0.07-0.15%, Al: 0.04-0.07%, Ti: 0.04-0.06%, P ⁇ 0.015%, S ⁇ 0.005%, N ⁇ 0.003%, the balance is Fe and unavoidable impurities, wherein the content of Al is greater than that of Ti.
  • the present invention finds that in the late stage of refining after deoxidation treatment, rare earth (Ce or La) is added to the molten steel, and the deoxidation product Al2O3 that does not exclude the molten steel reacts as follows:
  • n in the above formula are 11, 1, and 0; correspondingly, as the amount of rare earth added increases, the resulting reaction products are Re 2 O 3 ⁇ 11Al 2 O 3 (also known as ⁇ Al 2 O 3 ) , Re 2 O 3 ⁇ Al 2 O 3 (Ce 2 O 3 ⁇ Al 2 O 3 or La2O 3 ⁇ Al 2 O 3 ) and Re 2 O 3 ; the Ce in the product Re 2 O 3 ⁇ Al 2 O 3 2 O 3 ⁇ Al 2 O 3 is in liquid phase at 1600°C molten steel temperature, and in solid phase, the edges are smooth without obvious sharp angles, and the hardness is close to that of steel matrix.
  • the Al 2 O 3 crystals produced by conventional aluminum deoxidized steels belong to the ⁇ crystal form, which is a hexagonal crystal structure. It is a solid phase at the temperature of the molten steel, with sharp edges and a Mohs hardness of 9, which is much larger than other common materials.
  • the probability of mechanical damage to the steel plate matrix by the inclusions Re 2 O 3 ⁇ Al 2 O 3 in the titanium-containing ultra-low carbon steel of the present invention Greatly reduced, thereby reducing the degree of damage to the steel plate matrix and improving the surface quality of the finished product;
  • the typical inclusions in the cold-rolled finished product produced by the process of the present invention (the main component is confirmed to be Re 2 O 3 Al 2 O 3 ) are shown in Figure 3,
  • the single deoxidation product Al 2 O 3 in the cold-rolled finished product produced by the conventional process is given, as shown in Fig. 2 .
  • the composite inclusions produced under the control of the present invention have relatively smooth edges without obvious edges and corners, and the inclusions of the present invention tend to extend along the rolling direction after rolling, and have better plasticity.
  • titanium-containing ultra-low carbon steel causes nodules and is difficult to cast is that on the one hand, Ti in molten steel improves the wettability of the interface between the Al 2 O 3 surface layer and molten steel, thereby reducing the Al
  • the formation of the nodule position promotes the aggravation of nodulation.
  • test results conducted by the inventors show that: when the titanium-containing ultra-low carbon steel is smelted, when rare earth is added to the aluminum-deoxidized steel, the nozzle nodulation tends to intensify, and the crystallizer liquid level fluctuation rate increases, which seriously affects the continuous casting process
  • the forward movement reduces the proportion of qualified slabs and deteriorates the quality of finished products.
  • O/C mass ratio ⁇ 2.0 it is believed that oxygen in molten steel must ensure a sufficient excess (O/C mass ratio ⁇ 2.0) to maintain a high vacuum decarburization rate.
  • the present invention found that the initial oxygen-carbon mass ratio of vacuum decarburization in actual production is greater than 1.25, preferably greater than 1.27, for example greater than 1.3, and the carbon in molten steel can be reduced to below 10ppm within 17min.
  • the mass ratio of oxygen to carbon is less than 2.15, preferably less than 2.1, such as less than 2.0, so as to ensure that the oxygen content in the molten steel at the end of decarburization is less than 350ppm.
  • the vacuum refining decarburization treatment of the present invention makes the carbon in the molten steel below the required value of the finished product.
  • the free oxygen O in the molten steel is in the range of 100-350ppm; Decarburization time, the lower the free oxygen, the greater the decarburization time extension value; if the free oxygen after decarburization is higher than 350ppm, there are more deoxidized products in molten steel, the content of Al 2 O 3 in ladle slag is higher, and the crystallizer liquid level Volatility increased significantly.
  • the pure circulation time of the molten steel after aluminum addition and deoxidation is required to be ⁇ 3 minutes, so as to ensure that the deoxidation product Al2O3 in the steel fully floats up to the top slag of the ladle, so that most of the generated inclusions float up to the ladle top slag.
  • the composition of molten steel is adjusted to the target range, and the composition of oxide inclusions in the steel is controlled.
  • the circulation time of molten steel is ⁇ 2min, so that the number of residual inclusions in the molten steel is as small as possible.
  • Requirements about rare earth in the present invention 1) total oxygen T.O ⁇ 100ppm, which belongs to harmful components and will pollute molten steel, the lower the content, the better, so as to ensure the smooth flow of molten steel continuous casting; 2) N content ⁇ 30ppm, Control the content of titanium nitride in the finished product to be at a low level; 3) Other impurities in the rare earth except rare earth elements contain ⁇ 0.1wt%; achieve pouring straight, improve the performance of oxide inclusions, and reduce the titanium content of ultra-low carbon steel cold rolling The purpose of steel defects.
  • the preparation method of titanium-containing ultra-low carbon steel provided by the present invention effectively improves the performance of deoxidized inclusions in the steel, solves the problem of the casting of molten steel, reduces the incidence of cold rolling defects caused by Al 2 O 3 , and improves
  • the product quality of titanium-containing ultra-low carbon steel specifically includes the following beneficial effects:
  • the cold-rolling defect rate caused by Al 2 O 3 is lower than 0.05%, which is more than 90% lower than the conventional rare earth-free treatment process;
  • composition of oxide inclusions in steel changes from pure Al 2 O 3 to Re 2 O 3 Al 2 O 3 ;
  • the ratio of slab to steel is about 35% on average, which is better than the conventional rare earth-free treatment process (about 37% on average);
  • the vacuum refining time is less than 27 minutes, which is equivalent to the conventional rare earth-free treatment process
  • the consumption of titanium is lower than 0.7kg/t steel, which is equivalent to the conventional rare earth-free treatment process, and about 0.5kg/t steel less than the previous treatment process of adding titanium rare earth.
  • Fig. 1 is the schematic flow sheet of the preparation method of the titanium-containing ultra-low carbon steel of some embodiments of the present invention
  • Figure 2 is a schematic diagram of typical inclusions in cold-rolled finished steel under conventional processes
  • Fig. 3 is a schematic diagram of typical inclusions in the cold-rolled finished steel of the present invention.
  • Fig. 4 is a schematic diagram of crystallizer liquid level fluctuation coincidence rate
  • Figure 5 is a schematic diagram of the ratio of billet to steel.
  • the preparation method of titanium-containing ultra-low carbon steel provided by the present invention includes molten iron pretreatment, primary smelting in converter, vacuum refining, continuous casting, hot rolling, pickling and cold rolling; decarburization in vacuum refining
  • the free oxygen content in the molten steel is 100-350ppm, and then add Al for deoxidation treatment, the molten steel circulation time is ⁇ 3min; then add other alloys and rare earths to the molten steel, the molten steel circulation time is ⁇ 2min, and the final molten steel
  • the oxide Re 2 O 3 ⁇ Al 2 O 3 is formed in the process, and the vacuum refining is completed.
  • Other alloys added in vacuum refining are determined according to the composition of the specific finished steel product.
  • other alloys may include but not limited to one or more of alloying elements such as Mn, Nb, V, and B.
  • the molten iron is desulfurized by KR. After desulfurization, 3/4 of the top slag of the molten iron is removed; the S content in the molten iron after desulfurization is ⁇ 20ppm.
  • the converter adopts top-bottom combined blowing to ensure the strength of the bottom blowing.
  • the free oxygen content in the molten steel is ⁇ 600ppm;
  • the free oxygen O in the molten steel is between 100 and 350 ppm, and in some embodiments, the free oxygen O is between 100 and 300 ppm.
  • the applicable steel type is titanium-containing ultra-low-carbon steel products
  • this type of titanium-containing ultra-low-carbon steel includes the following components by mass percentage: C ⁇ 0.005%, Si ⁇ 0.05%, Mn: 0.05 ⁇ 0.3%, Al: 0.04 ⁇ 0.15%, Ti: 0.04 ⁇ 0.1%, P ⁇ 0.05%, S ⁇ 0.02%, N ⁇ 0.003%, the balance is Fe and unavoidable impurities
  • the content of Al is greater than that of Ti, so as to ensure that the final deoxidation of the molten steel is controlled by Al in the molten steel before the rare earth is added.
  • the preparation method of the titanium-containing ultra-low carbon steel of the present invention is further introduced in conjunction with specific examples below; wherein the following components of the titanium-containing ultra-low carbon steel in the embodiments are: C ⁇ 0.0018%, Si ⁇ 0.03%, Mn: 0.07 ⁇ 0.15%, Al: 0.04 ⁇ 0.07%, Ti: 0.04 ⁇ 0.06%, P ⁇ 0.015%, S ⁇ 0.005%, N ⁇ 0.003%, the balance is Fe and unavoidable impurities, the content of Al Greater than Ti content;
  • the process path adopted in this embodiment is molten iron pretreatment (hot metal desulfurization, dephosphorization) ⁇ converter primary smelting (converter top-bottom combined blowing smelting, tapping) ⁇ ladle top slag modification ⁇ vacuum refining (decarburization, deoxidation, alloying chemical and rare earth treatment) ⁇ continuous casting ⁇ hot rolling ⁇ pickling ⁇ cold rolling;
  • the coincidence rate of ⁇ 5mm of liquid level fluctuation in the crystallizer is 94.2%, and the coincidence rate of ⁇ 5mm of liquid level fluctuation is 36%; 40%, and the steel defect rate caused by Al 2 O 3 is 0.02%.
  • Table 1 and table 2 are other situations of applying the program example of the present invention in actual production, contrast I group adopting titanium pre-deoxidation rare earth treatment and contrast II group adopting the situation comparison of conventional non-rare earth treatment;
  • contrast I group comparativative examples 1 ⁇ 6
  • process molten iron pretreatment (desulfurization, dephosphorization) ⁇ primary smelting (converter top-bottom blowing smelting, tapping) ⁇ ladle top slag modification ⁇ vacuum refining (decarburization, titanium pre-deoxidation, Al deoxidation, alloying and rare earth treatment) ⁇ continuous casting ⁇ hot rolling ⁇ pickling ⁇ cold rolling
  • comparison group II comparativative examples 7 to 12) process: molten iron pretreatment (desulfurization, dephosphorization) ⁇ primary smelting (converter top and bottom combined blowing smelting, tapping) ⁇ Ladle top slag modification ⁇ vacuum refining (decarburization, Al deoxidation, alloying) ⁇ continuous
  • the crystallizer liquid level fluctuates The coincidence rates of ⁇ 5mm and ⁇ 3mm are >92% and >32%, respectively, which are superior to the conventional rare earth-free treatment process;
  • the oxide inclusion composition of the titanium-containing ultra-low carbon steel of the present invention is transformed from pure Al 2 O 3 to Re 2 O 3 Al 2 O 3 ;
  • the titanium-containing ultra-low carbon steel of the present invention has an average ratio of slab to steel of about 35%, which is better than the conventional rare earth-free treatment process (average about 37%);
  • the vacuum refining time is less than 27min, which is different from the conventional non- The rare earth treatment process is equivalent;
  • the titanium consumption is equivalent to the conventional rare earth-free treatment process, which is about 0.5kg/t steel less than the previous rare earth treatment process with titanium addition.
  • the titanium-containing ultra-low carbon steel produced by the present invention has the same vacuum refining time as the titanium consumption and conventional rare earth-free treatment, and can ensure that the continuous casting process goes smoothly and greatly reduces the occurrence of cold rolling defects caused by Al 2 O 3 rate (reduction > 90%), significantly improving the product quality of titanium-containing ultra-low carbon steel;
  • the preparation method of titanium-containing ultra-low carbon steel of the present invention effectively improves the performance of deoxidized inclusions in the steel, solves the problem of continuous casting of molten steel, and reduces the amount of Al 2 O 3
  • the occurrence rate of cold-rolling defects caused by it is suitable for improving the quality of titanium-containing ultra-low carbon steel cold-rolled products, and has the value of popularization and application in steelmaking plants.

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PCT/CN2022/101860 2021-06-29 2022-06-28 一种含钛超低碳钢的制备方法 WO2023274223A1 (zh)

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CN112442631A (zh) * 2019-08-30 2021-03-05 宝山钢铁股份有限公司 一种含钛超低碳钢冷轧钢质缺陷的控制方法
CN112342333A (zh) * 2020-11-06 2021-02-09 马鞍山钢铁股份有限公司 一种高效、低氧位超低碳钢生产方法

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