CN110205443B - Ultralow-oxygen smelting method for low-carbon silicon-aluminum-containing killed steel - Google Patents
Ultralow-oxygen smelting method for low-carbon silicon-aluminum-containing killed steel Download PDFInfo
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Abstract
The invention belongs to the technical field of steelmaking processes, and relates to an ultralow-oxygen smelting method for low-carbon silicon-aluminum-containing killed steel. Refining by adopting conventional alkalinity (R is 5.0-10.0), and controlling the type and adding time of the alloy to inhibit Al in the LF process2O3The purpose of converting inclusions into calcium aluminate is achieved, thereby realizing Al in the steel before the refining is finished2O3Controlling inclusions, and then efficiently removing Al by RH vacuum2O3The content of impurities is controlled within 8 ppm.
Description
Technical Field
The invention belongs to the technical field of steelmaking processes, and particularly relates to a silicon-aluminum-containing deoxidized steel ultra-low oxygen smelting control method.
Background
With the development of steel smelting technology, the requirement on molten steel cleanliness is higher and higher, and particularly the requirement on inclusions is higher for automobile steel. In the case of high-carbon steel, since the content of dissolved oxygen can be further reduced by molten steel C under vacuum conditions, the total oxygen (T.O) of high-carbon steel such as GCr15 can be easily controlled within 8ppm by using the LF-RH refining process. But for low carbon steel with less than 0.25% of C, the same production process is adopted, and the finished product T.O is only controlled to 10-15 ppm and is difficult to control within 8 ppm.
Through retrieval, patents and papers published at home and abroad mainly reduce the total oxygen content of molten steel from strengthening LF refining such as adopting high-alkalinity high-reducibility refining slag, strengthening RH vacuum operation such as delaying vacuum treatment time, controlling high vacuum degree and the like. Chinese patent application No. CN201110403479.X 'production method of ultralow-oxide inclusion steel' proposes that ultralow-oxygen steel is produced by adopting an RH-LF-RH refining process, and although the total oxygen of bearing steel can be controlled to 5ppm by adopting the method, the process is complicated, the production cost is high, and the method is difficult to be widely applied to industrial production. Chinese patent application No. CN201811167952.7, "a bearing steel liquid deoxidation control method without Ds-type inclusions", indicates that T.O can be controlled below 10ppm when low-aluminum-content bearing steel is produced by using low-alkalinity refining slag. The method is only suitable for high-carbon bearing steel, and the dissolved oxygen is reduced by using carbon under the vacuum condition, so that the purpose of controlling T.O is finally achieved. For low carbon steel, ultra-low oxygen smelting is difficult to achieve by adopting the method. Chinese patent application No. CN201310456419.3, "a smelting method of steel for HIC/SSCC resistance", proposes to use high alkalinity high reducing refining slag, which first denatures inclusions in LF process into liquid calcium aluminate, and then removes the liquid calcium aluminate with RH to achieve the purpose of ultra-low oxygen smelting, and this method considers that the liquid calcium aluminate is easier to remove from the molten steel, but the wetting angle between the liquid inclusions and the molten steel is significantly lower than that of the solid inclusions, i.e. the liquid calcium aluminate inclusions are more difficult to remove than the solid inclusions, so it is difficult to control the t.o of low carbon steel to below 8ppm by using this method. The document "Investigation on the removal efficiency of solids in Al-kill liquid in differential removal processes" indicates solid Al2O3The removal efficiency of the inclusions in the RH process is far higher than that of calcium aluminate, and the inclusions are easily removed by Al because the slag steel reaction in the LF process is difficult to avoid2O3Is converted into calcium aluminate, so that Al is used as the inclusion before RH vacuum treatment2O3It is proposed to adopt BThe OF-RH-CC process is used for producing low-carbon pipeline steel. However, for most steel grades, an LF refining furnace is omitted, and the temperature of molten steel after RH treatment cannot meet the continuous casting requirement easily, so that many steel grades need to be subjected to LF treatment before RH treatment. However, if LF refining is used first, the inclusions are easily formed of Al2O3The conversion into calcium aluminate does not have corresponding patent or literature to provide Al for inhibiting LF process2O3A process for converting to calcium aluminate. Based on the control difficulty, the Chinese patent application No. CN201611126263.2 'a process for smelting pipeline steel for improving the purity of molten steel' proposes blowing oxygen into the molten steel in RH vacuum treatment, and the operation can convert calcium aluminate into Al again2O3But due to Al after oxygen blowing2O3The number density of inclusions is sharply increased, and thus, the vacuum treatment time must be additionally prolonged to remove most of Al from the molten steel2O3And then removed.
Therefore, aiming at producing low-carbon silicon-aluminum-containing killed steel by adopting BOF-LF-RH-CC process, the invention provides Al for inhibiting LF process2O3The method for converting the inclusion into calcium aluminate and then efficiently removing Al by means of RH vacuum2O3And the impurities are included, and the purpose of ultra-low oxygen smelting is finally realized.
Disclosure of Invention
The invention aims to develop an ultra-low oxygen smelting method of low-carbon silicon-aluminum-containing killed steel, which can replace the traditional smelting method, easily realize the ultra-low oxygen smelting of the low-carbon steel and obviously improve the quality grade of products.
The steel comprises, by mass, 0.05-0.25% of C, 0.15-0.25% of Si, 0.3-1.5% of Mn, 0.005-0.015% of S, 0.015-0.04% of Al, and the balance of iron and residual elements.
The ultralow-oxygen smelting method of the low-carbon silicon-aluminum-containing killed steel is characterized by comprising the following key points:
firstly, controlling the end point temperature of the converter to be 1610-1660 ℃, and controlling the end point S to be less than 0.015%; 130kg of aluminum cakes are added for deoxidation during converter tapping, ferromanganese and a low-nitrogen carburant are added for alloying, silicon-containing alloy such as ferrosilicon, silicomanganese and electrolytic silicon is not added during tapping, and 600 kg/furnace lime and 100 kg/furnace fluorite are added for slagging after the alloy is added.
And secondly, heating the molten steel for 6-10 min when the LF enters the station, sampling the molten steel when the temperature is raised to be more than 1550 ℃, analyzing components, feeding back a component detection result to the operation chamber, adding aluminum particles into the molten steel to control the Al content of the molten steel to be 0.025-0.05%, adding ferromanganese and a low-nitrogen carburant to adjust the Mn and C content, controlling the alkalinity of the refining slag to be 5.0-10.0, and controlling the (TFe + MnO) content in the slag to be less than 1.20%. And in the LF process, no silicon-containing alloy such as ferrosilicon, silicomanganese and electrolytic silicon is added, and if the Al content of the molten steel is low in the last stage of LF, aluminum particles can be continuously added to adjust the Al content of the molten steel to be 0.030-0.045%. The flow rate of argon blowing at the bottom of the steel ladle is controlled to be below 400L/min.
And (III) RH enters a station and is vacuumized, electrolytic silicon is added into the vacuum chamber when the vacuum degree is below 3000Pa, the electrolytic silicon is added in place at one time, then no alloy or slag is added, the total vacuum treatment time is controlled to be 20-25 min, a small amount of calcium treatment is carried out after the vacuum treatment, and the soft blowing time is more than or equal to 15 min.
And (IV) the continuous casting adopts full-process protection casting.
After the applicant researches the removal efficiency of different types of inclusions in the RH process, solid inclusions, particularly solid Al, are found2O3The removal efficiency of the impurities is far higher than that of liquid impurities. In the conventional LF-RH refining process, although the inclusions before LF treatment are Al2O3However, by LF treatment, the inclusions are easily converted to calcium aluminate, thus reducing their removal efficiency during the subsequent RH process. In addition, through the results of earlier research and industrial experiments, the Si content of the ferrosilicon alloy and the molten steel can promote Al in the LF process2O3The transformation of the inclusion to calcium aluminate is realized because the ferrosilicon produced in China contains a small amount of metallic calcium, and meanwhile, under the condition of bottom blowing Ar to the LF ladle, the Si content of the molten steel can promote the slag steel reaction to lead the slag to transfer calcium into the molten steel, so that the inclusion in the steel is still Al when the refining is finished2O3Without any addition of silicon-containing alloys during tapping and LF, and based onThe reaction of slag steel is very weak in the RH process, and electrolytic silicon is added in the RH vacuum treatment for Si alloying. Because no silicon-containing alloy is added in the tapping and LF processes, the Si content of the molten steel in the LF process is very low, and therefore, Al in the LF process can be inhibited by adopting the conventional slag alkalinity2O3The transformation of the inclusion to calcium aluminate finally realizes the Al in the steel at the end of the LF2O3Controlling the inclusions.
According to the ultralow-oxygen smelting method for the low-carbon silicon-aluminum-containing killed steel, the end point S in the step (I) is controlled to be below 0.015%, and the desulfurization burden in the LF process is mainly relieved. No silicon-containing alloy is added in the step (I) and the step (II), and the Si content of the molten steel can promote the slag steel reaction in the LF process, so that the calcium is increased in the molten steel. And (C) adopting electrolytic silicon to carry out Si alloying in the step (III), mainly because the common ferrosilicon alloy contains a small amount of metallic calcium.
Because the invention realizes the ultra-low oxygen smelting when the RH is broken, a small amount of calcium silicate wire can be fed after the RH is broken to ensure the castability of the molten steel, and the calcium treatment process does not influence the total oxygen value of the finished product. The production practice tests show that the total oxygen of the finished product can be controlled within 8ppm by implementing the method of the invention.
The invention has the advantages that the type, the adding time and the like of the ferrosilicon alloy are controlled, so that the inclusions at the end of refining can be controlled to be Al2O3And part of the inclusions contain a small amount of CaO and MgO, so that the purpose of ultra-low oxygen smelting is realized through subsequent RH vacuum, T.O can be controlled below 8ppm, B and Ds inclusions of steel can be controlled at 0.5 level or even 0 level, and the economic effect is obvious.
Drawings
FIG. 1 is a graph showing the analysis of inclusions in LF end steel of example 1;
FIG. 2 is a graph showing the analysis of inclusions in LF end steel of example 2;
FIG. 3 is a graph showing the analysis of inclusions in LF finish steel of comparative example 1;
FIG. 4 is a graph showing the analysis of inclusions in LF finish steel of comparative example 2.
Detailed Description
The 20-ton steel is produced by adopting a 130-ton converter, a 130-ton refining furnace and a 130-ton RH furnace.
Example 1:
the finished steel comprises the following components: 0.21%, Si 0.18%, Mn 0.40%, S0.009%, and Al 0.025%.
A top-bottom combined blown converter is adopted, the raw materials are molten iron and scrap steel, the ratio of the scrap steel is 15%, the carbon content after the molten iron is pretreated is 4.12%, and the sulfur content is 0.003%. The converter adopts a conventional blowing method, the end point temperature of the converter is controlled at 1638 ℃, the end point S is controlled at 0.012%, the end point C content is 0.085%, 130kg of aluminum cake, 400kg of low-carbon ferromanganese and 50kg of low-nitrogen carburant are added during converter tapping, and then 600kg of lime and 100kg of fluorite are added.
Heating the molten steel 10min before LF, heating to 1554 ℃ for sampling the molten steel, feeding back a component detection result 8min after sampling to a main control room, adding 150kg of aluminum particles, 120kg of low-carbon ferromanganese and 110kg of low-nitrogen carburant, and controlling the flow of bottom blowing Ar in the whole process to be 300-400L/min. 30kg of aluminum particles are added in the final stage of LF, and the Al content is 0.039% after refining.
The composition of the slag at the end of LF is shown in Table 1 (unit:%):
table 1:
the inclusion in the LF end steel is solid Al2O3The inclusions contain small amounts of MgO and CaO, as shown in FIG. 1:
210kg of electrolytic silicon is added into a vacuum chamber when the RH vacuum degree is 1000Pa, then no alloy or slag is added, the total vacuum treatment time is controlled to be 24min, a 50m calcium-silicon wire is fed after the vacuum treatment, and the soft blowing time is 18 min.
The continuous casting adopts the whole-course protection casting.
The total oxygen content of the molten steel in the smelting process is changed into that the total oxygen content at the end of LF is 19.7ppm, the total oxygen content of RH broken space is 7.6ppm, and the total oxygen content of the finished product is 7.2 ppm.
The low carbon steel prepared in the example 1 is subjected to inclusion detection, and the GB/T10561 test standard is adopted, and the inclusion rating is as follows:
the steel materials are in B coarse 0 grade, B fine 0 grade, C coarse 0 grade, C fine 0 grade, D coarse 0.5 grade, D fine 0.5 grade and Ds0.5 grade.
Example 2:
the finished steel comprises the following components: 0.20%, Si 0.21%, Mn 0.43%, S0.006%, and Al 0.028%.
A top-bottom combined blown converter is adopted, the raw materials are molten iron and scrap steel, the ratio of the scrap steel to the molten iron is 17%, the carbon content after the molten iron is pretreated is 4.07%, and the sulfur content is 0.004%. The converter adopts a conventional blowing method, the end point temperature of the converter is controlled to be 1647 ℃, the end point S is controlled to be 0.014%, the end point C content is 0.097%, 130kg of aluminum cake, 400kg of low-carbon ferromanganese and 50kg of low-nitrogen carburant are added during converter tapping, and then 600kg of lime and 100kg of fluorite are added.
Heating the molten steel 7min before LF, heating to 1558 ℃ for sampling the molten steel, feeding back a component detection result 6min after sampling to a main control room, adding 120kg of aluminum particles, 140kg of low-carbon ferromanganese and 130kg of low-nitrogen carburant, and controlling the flow of bottom blowing Ar in the whole process to be 300-400L/min. And adding 50kg of aluminum particles in the final stage of LF, wherein the Al content is 0.044% after refining.
The composition of the slag at the end of LF is shown in Table 2 (unit:%):
table 2:
the inclusion in the LF end steel is solid Al2O3The inclusions contain small amounts of MgO and CaO, as shown in FIG. 2:
220kg of electrolytic silicon is added into a vacuum chamber when the RH vacuum degree is 1000Pa, then no alloy or slag is added, the total vacuum treatment time is controlled to be 23min, a 50m calcium-silicon wire is fed after the vacuum treatment, and the soft blowing time is 21 min.
The total oxygen change of the molten steel in the smelting process is 17.6ppm of total oxygen at the end of LF, 7.1ppm of total oxygen in RH vacuum, and 7.3ppm of total oxygen of finished products.
The continuous casting adopts the whole-course protection casting.
The low carbon steel prepared in the example 2 is subjected to inclusion detection, and the GB/T10561 test standard is adopted, and the inclusion rating is as follows:
the steel materials are in B coarse 0.5 grade, B fine 1.0 grade, C coarse 0 grade, C fine 0 grade, D coarse 0.5 grade, D fine 0.5 grade and Ds0 grade.
Comparative example 1
The finished steel comprises the following components: 0.20%, Si 0.20%, Mn 0.40%, S0.005%, and Al 0.026%.
A top-bottom combined blown converter is adopted, the raw materials are molten iron and scrap steel, the ratio of the scrap steel is 16%, the carbon content after the molten iron is pretreated is 3.92%, and the sulfur content is 0.003%. The converter adopts a conventional blowing method, the end point temperature of the converter is controlled to be 1629 ℃, the end point S is controlled to be 0.011 percent, the end point C content is 0.078 percent, 130kg of aluminum cakes, 350kg of ferrosilicon, 480kg of low-carbon ferromanganese and 50kg of low-nitrogen carburant are added in the converter steel tapping, and then 600kg of lime and 100kg of fluorite are added.
Heating the molten steel 8min before LF, heating to 1553 ℃ for sampling the molten steel, feeding back a component detection result 7min after sampling to a main control room, adding 140kg of aluminum particles, 80kg of low-carbon ferromanganese and 110kg of low-nitrogen carburant, and controlling the flow of bottom blowing Ar in the whole process to be 300-400L/min. And 20kg of aluminum particles are added in the final stage of LF, and the Al content is 0.041% after refining.
The composition of the slag at the end of LF is shown in Table 3 (unit:%):
table 3:
CaO-Al in liquid or semi-liquid state as inclusion in LF end steel2O3MgO, as shown in FIG. 3:
RH does not add any alloy and slag charge, the vacuum treatment time is 22min, the silicon-calcium wire of 50m is fed after the vacuum treatment, and the soft blowing time is 25 min.
The total oxygen change of the molten steel in the smelting process is 16.7ppm of total oxygen at the end of LF, 12.5ppm of total oxygen in RH vacuum, and 12.1ppm of total oxygen of a finished product.
The continuous casting adopts the whole-course protection casting.
The steel prepared in the comparative example 1 is detected for inclusions, and the inclusion rating is as follows by adopting a GB/T10561 test standard:
the steel materials are in B coarse grade 1.0, B fine grade 1.5, C coarse grade 0, C fine grade 0, D coarse grade 1.0, D fine grade 1.0 and Ds1.5.
Comparative example 2
The finished steel comprises the following components: 0.22 percent, 0.18 percent of Si, 0.41 percent of Mn, 0.006 percent of S and 0.029 percent of Al.
A top-bottom combined blown converter is adopted, the raw materials are molten iron and scrap steel, the ratio of the scrap steel to the molten iron is 17%, the carbon content after the molten iron is pretreated is 4.10%, and the sulfur content is 0.003%. The converter adopts a conventional blowing method, the end point temperature of the converter is controlled to be 1622 ℃, the end point S is controlled to be 0.014%, the end point C content is 0.095%, 130kg of aluminum cakes, 480kg of low-carbon ferromanganese and 50kg of low-nitrogen carburant are added in the converter steel tapping, and then 600kg of lime and 100kg of fluorite are added.
Heating the molten steel 10min before LF, heating to 1561 ℃ for sampling the molten steel, feeding back a component detection result 8min after sampling to a main control room, adding 150kg of aluminum particles, 95kg of low-carbon ferromanganese and 120kg of low-nitrogen carburant, and controlling the flow of bottom blowing Ar in the whole process to be 300-400L/min. LF treatment is carried out for about 30min, and 360kg of ferrosilicon alloy is added. 35kg of aluminum particles are added in the final stage of LF, and the Al content is 0.044% after refining.
The composition of the slag at the end of LF is shown in Table 4 (unit:%):
table 4:
CaO-Al in liquid or semi-liquid state as inclusion in LF end steel2O3MgO, as shown in FIG. 4:
RH does not add any alloy and slag charge, the vacuum treatment time is 20min, the silicon-calcium wire of 50m is fed after the vacuum treatment, and the soft blowing time is 28 min.
The total oxygen change of the molten steel in the smelting process is 17.2ppm of total oxygen at the end of LF, 13.1ppm of total oxygen in RH vacuum, and 13.2ppm of total oxygen of finished products.
The continuous casting adopts the whole-course protection casting.
The steel prepared in the comparative example 2 is detected for inclusions, and the inclusion rating is as follows by adopting the GB/T10561 test standard:
the steel materials are in B coarse grade 1.0, B fine grade 2.0, C coarse grade 0, C fine grade 0, D coarse grade 1.0, D fine grade 1.0 and Ds1.5.
Claims (5)
1. The ultralow-oxygen smelting method of the low-carbon silicon-aluminum-containing killed steel is characterized in that the low-carbon steel is smelted by adopting a BOF-LF-RH-CC process, and comprises the following steps:
(1) the converter adopts a conventional blowing method, the end point temperature of the converter is controlled to be 1610-1660 ℃, and the end point S is controlled to be below 0.015 percent;
(2) adding aluminum for deoxidation during converter tapping, then adding ferromanganese and a low-nitrogen recarburizing agent for alloying, and then adding lime and fluorite for slagging;
(3) in the LF process, a deoxidizer is not required to be added on the slag surface for deoxidizing the slag surface, the content of (TFe + MnO) in the slag is mainly controlled by reacting with Al in molten steel, the alkalinity of refined slag is controlled to be 5.0-10.0, and the Al content is controlled to be 0.030-0.045% after refining; no silicon-containing alloy is added in the tapping in the step (2) and the LF in the step (2), and the inclusion is controlled to be Al when the LF refining is finished2O3；
(4) Starting RH station entering and vacuumizing, adding electrolytic silicon into a vacuum chamber under the vacuum degree of 3000Pa, then adding no alloy and slag, and controlling the total vacuum treatment time to be 20-25 min;
(5) the continuous casting adopts the whole-course protection casting.
2. The smelting method of the ultralow-oxygen and medium-low-carbon steel according to claim 1, characterized by comprising the following steps: the low-carbon steel product comprises the following components: 0.05-0.25% of C, 0.15-0.25% of Si, 0.3-1.5% of Mn, 0.005-0.015% of S, 0.015-0.04% of Al, and the balance of iron and residual elements.
3. The method for smelting low-carbon steel by ultra-low oxygen according to claim 1, characterized by comprising the following steps: and (4) in the LF process of the step (3), controlling the whole process of bottom blowing argon flow to be below 400L/min.
4. The method for smelting low-carbon steel by ultra-low oxygen according to claim 1, characterized by comprising the following steps: all the electrolytic silicon is added in the step (4), and no silicon-containing alloy is added in the tapping and LF processes; the silicon-containing alloy is ferrosilicon, silicomanganese or electrolytic silicon.
5. The ultra-low oxygen smelting method of the low-carbon silicon-aluminum-containing killed steel as claimed in claim 1, characterized by comprising the following steps: and (4) carrying out a small amount of calcium treatment after vacuum treatment in the step (4), wherein the soft blowing time is more than or equal to 15 min.
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| CN110983161B (en) * | 2019-12-05 | 2021-03-23 | 中天钢铁集团有限公司 | Smelting method for realizing ultrahigh purity of bearing steel by controlling adding time of low-aluminum low-titanium ferrosilicon and combining with tundish electromagnetic stirring |
| CN114807491B (en) * | 2021-01-28 | 2024-01-05 | 上海梅山钢铁股份有限公司 | Production method of ultra-low oxygen and sulfide high spheroidization rate medium and low carbon steel molten steel |
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| CN113584257B (en) * | 2021-08-03 | 2022-12-02 | 攀钢集团西昌钢钒有限公司 | Method for efficient and economic sedation and aluminum alloying of aluminum killed steel |
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