CN110293219B - Method for reducing large-size calcium aluminate inclusion in steel - Google Patents
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- CN110293219B CN110293219B CN201910574074.9A CN201910574074A CN110293219B CN 110293219 B CN110293219 B CN 110293219B CN 201910574074 A CN201910574074 A CN 201910574074A CN 110293219 B CN110293219 B CN 110293219B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
- B22D41/50—Pouring-nozzles
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- B22D41/54—Manufacturing or repairing thereof characterised by the materials used therefor
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a method for reducing large-size calcium aluminate inclusion in steel by controlling Al2O3Decarburization of refractory of-C submerged entry nozzleThe depth is increased, so that the aim of reducing large-size calcium aluminate inclusions is fulfilled; the continuous casting refractory material is a tundish submerged nozzle, and the main components of the submerged nozzle refractory material are alumina and carbon; during steel-making production, Al is controlled2O3The decarburization depth of the refractory of the C-quality submerged nozzle is reduced to reduce large-size calcium aluminate inclusions. The steel grade produced by the method can greatly reduce the amount of large-size calcium aluminate and improve the quality of steel products.
Description
Technical Field
The invention relates to a method for reducing large-size calcium aluminate inclusions in steel.
Background
The large-size calcium aluminate inclusion in the steel has influence on a plurality of steel products, so that the technical requirements on the calcium aluminate inclusion in the steel are provided for bearing steel, pipeline steel and the like. In order to reduce or even eliminate large-size calcium aluminates, a number of metallurgists have performed relevant work.
Through retrieval, patents on reducing large-size calcium aluminate inclusion in steel at home and abroad mainly focus on controlling a molten steel deoxidation mode, such as a bearing steel molten steel deoxidation control method without Ds type inclusion and a bearing steel smelting process beneficial to controlling inclusion, wherein a conventional aluminum deoxidation process is changed into a silicon deoxidation process, so that the size and the number of the calcium aluminate inclusion are reduced;
through retrieval, the domestic and foreign documents about reducing large-size calcium aluminate inclusion in steel mainly focus on the aspects of optimizing the calcium treatment amount in the refining process, controlling the alkalinity of slag, controlling continuous casting connection blanks and the like; as described in "study on non-metallic inclusions in LF refining of Low carbon and aluminum killed Steel", it is suggested that the calcium treatment causes the size of calcium aluminate inclusions to increase, and therefore, it is claimed that the molten steel is subjected to slight or no calcium treatment after refining, and the influence of slag basicity on Ds inclusions in low carbon steel "mentioned that the size of calcium aluminate is controlled by controlling the slag basicity, and" origin of metal cast における in mesh department "mentioned that large-size calcium aluminate comes from slag mixed-flushing in the ladle changing process, and continuous casting billets should be controlled. The influence of the refractory material on inclusions in steel is researched in 'the influence and optimization of steel ladle refractory material on inclusions in steel', but the influence is mainly concentrated on oxygen content, sulfide inclusions, silicate inclusions and alumina inclusions in steel, large-size calcium aluminate inclusions in molten steel are not explained, and on the other hand, the large-size inclusions generated in the refining process can quickly float upwards and be removed in the smelting process and the subsequent soft blowing process, so that a large amount of large-size inclusions cannot be generated in the process and are left in subsequent products.
The invention relates to a method for reducing large-size calcium aluminate inclusion in steel, which controls Al2O3The decarburization depth of the refractory material of the C-quality submerged nozzle is less than or equal to 1.5mm, so that the method for reducing large-size calcium aluminate inclusions in steel is achieved.
Disclosure of Invention
The invention aims to develop a method for reducing large-size calcium aluminate inclusions in steel, and under the condition that other process conditions are not changed, the method can well reduce the number of the large-size calcium aluminate inclusions in the steel and improve the cleanliness of steel.
The invention provides a calcium aluminate clamp for reducing large size in steelMethod of impurities by controlling Al2O3The decarburization depth of the refractory material of the C-quality submerged nozzle is made to be less than or equal to 1.5mm, so that the quantity of large-particle calcium aluminate inclusions is controlled.
The control method comprises the following main points:
the invention relates to a continuous casting refractory material which is a tundish submerged nozzle and is made of Al2O3A substance C of which Al is2O3More than or equal to 50 percent and C more than or equal to 1 percent; by controlling Al2O3The decarburization depth of the refractory material of the C-quality submerged nozzle is less than or equal to 1.5mm, so that the number of large-size calcium aluminate inclusions is reduced.
Further, the invention controls the decarburization depth of the refractory material of the submerged nozzle through a baking system,
further, the baking process comprises the following steps:
selection of Al2O3The submerged nozzle of the C-quality tundish is required to be baked for 3-5 hours in total, the submerged nozzle is firstly baked for 1-1.5 hours, and the temperature of the submerged nozzle of the tundish is required to be kept at 100 ℃ within 1-1.5 hours; then rapidly heating to 600-800 ℃ at the heating rate of 30 ℃/min, heating to 600-800 ℃, and preserving heat for 0.5-3 h; after heat preservation, the temperature is raised to 900 ℃ and the temperature is preserved for 1h at 900 ℃.
The invention controls the baking time and the baking temperature of the submerged nozzle of the tundish to ensure that Al is contained2O3The decarburization depth of the-C submerged nozzle refractory material is less than or equal to 1.5mm after use, so that the purpose of reducing large-size calcium aluminate inclusions in steel is achieved.
Because the generation of large-size calcium aluminate in steel is manifold, if large-size calcium aluminate inclusion is generated in steel in a refining process or a more previous production process, the floating removal can be completed by a soft blowing process; however, in the continuous casting process, because the molten steel rapidly passes through the submerged nozzle of the tundish and then enters the crystallizer, if large-size calcium aluminate inclusion is generated at the submerged nozzle of the tundish, the large-size calcium aluminate inclusion is captured by the continuous casting billet quickly without the time of floating and removing at all, and is left in the steel product, and finally the quality of the product is influenced. Based on the mechanism, the aim of reducing large-size calcium aluminate in steel is achieved by controlling the baking system of the refractory material of the immersion water (the most fundamental control method is to control the decarburization of the refractory material).
The reason why the method of the present invention for reducing large-size calcium aluminate inclusions in steel by controlling decarburization of the refractory will be described in detail below. As will be understood from the continuous casting production schematic view shown in fig. 1, the molten steel from the tundish can reach the mold only after flowing through the tundish submerged nozzle, and is finally cooled by the mold and the like to form a continuous cast slab.
When molten steel passes through a tundish submerged nozzle, calcium in the steel and small-size calcium aluminate inclusions in the steel react with refractory materials, and the reaction is carried out according to the following steps (1) and (2); after the reaction, calcium aluminate inclusions generated by the reaction are gathered at the inner wall of the refractory material, and when the gathered calcium aluminate inclusions reach a certain size, the calcium aluminate inclusions leave the refractory material and enter molten steel to become large-size calcium aluminate inclusions.
Ca(calcium in molten Steel)+Al2O3 (refractory material)→CaO-Al2O3 (calcium aluminate inclusions)…………………………(1)
CaO-Al2O3 (calcium aluminate inclusion in molten steel)+Al2O3 (refractory material)→CaO-Al2O3 (calcium aluminate inclusions)…………(2)
Therefore, the reaction of the molten steel and the calcium aluminate inclusion in the molten steel with the refractory material is reduced, and the calcium aluminate inclusion generated by the refractory material can be reduced; however, all molten steel can enter the crystallizer only through a submerged nozzle of the tundish, so the invention reduces the generation of large-size calcium aluminate in steel by controlling the contact area of the molten steel and calcium aluminate inclusions in the molten steel and refractory materials.
As shown in FIG. 2, it is understood that the decarburization and non-decarburization of the refractory are schematically shown, and when the decarburization of the refractory does not occur, the contact probability and area between the molten steel and the alumina in the refractory are small, because the carbon in the refractory acts as a barrier and the smooth wall surface is much smaller in specific surface area; if the hard material is decarburized once, the wall surface becomes very rough, and a large amount of molten steel enters the hard material decarburization channel and reacts with alumina in the hard material, so that the reaction specific surface area after decarburization is greatly increased. From the above analysis, it is known that after decarburization occurs in the submerged nozzle of the continuous casting tundish, the contact reaction area between the molten steel and the refractory is greatly increased, the generation of calcium aluminate is promoted, and finally, large-size calcium aluminate inclusions in the steel are increased.
Drawings
FIG. 1 is a schematic illustration of a continuous casting process;
FIG. 2 is a schematic diagram showing a comparison between the reaction of molten steel and decarburization resistant materials;
FIG. 3 is an electron micrograph of a decarburized layer after molten steel is poured through a tundish immersion nozzle in accordance with example 1;
FIG. 4 is an electron micrograph of a decarburized layer after molten steel is poured by a tundish immersion nozzle in comparative example 1.
Detailed Description
The method for reducing large-size calcium aluminate inclusions in steel by controlling the decarburization of a tundish submerged nozzle according to the present invention will be described in detail below.
Because the tundish must be baked before use, and the baking system can influence the decarburization depth of a tundish submerged nozzle, in the field, the baking effect and the baking purpose are different, some tundishes are only baked with small fire for drying, and some steel mills need to be quickly baked to 1000-1100 ℃, so that the heat stability is improved, and the service life is prolonged. In the art, the decarburisation depth after use of common toasting regimes all exceeded 1.5mm, and toasting Al was not recognized primarily2O3The submerged nozzle system of the C-type tundish influences the decarburization depth, so that the size and the quantity of large-size calcium aluminate inclusions in molten steel are influenced. The application provides a method for reducing large-size calcium aluminate inclusions in steel by reducing the decarburization of a tundish submerged nozzle through a baking process for the first time.
The method specifically comprises the following steps: during the test, Al was selected2O3-CThe refractory material for the immersed nozzle of the tundish is required to be baked for 3-5 h in total, the baking is firstly carried out for about 1-1.5 h, and the temperature of the immersed nozzle of the tundish is required to be kept at about 100 ℃ within 1-1.5 h; then rapidly heating to 600-800 ℃, wherein the heating rate is 30 ℃/min, heating to 600-800 ℃ and preserving heat for 0.5-3 h; after heat preservation, the temperature is raised to 900 ℃ again, the temperature rise rate is 30 ℃/min, the heat preservation is carried out for about 1h, the baking is finished, and the Al is ensured2O3The decarburization depth of the inner wall of the refractory material of the submerged nozzle of the-C tundish is less than or equal to 1.5 mm.
According to the invention, the decarburization depth of the submerged nozzle is controlled by changing the baking system, so that the data of the number of large-particle calcium aluminate inclusions in the steel under different decarburization depths of the submerged nozzle are obtained. The key point of controlling the decarburization of the submerged nozzle by controlling the baking of the tundish lies in controlling the time of the refractory material in the temperature interval easy to decarbonize, and the Al is2O3The refractory material of the C-quality submerged nozzle belongs to the easy decarburization temperature range from 600 ℃ to 800 ℃, and the decarburization depth of the final refractory material can be well controlled by controlling the time of the refractory material in the easy decarburization range from 600 ℃ to 800 ℃. The highest baking temperature is controlled at 900 ℃, although the highest baking temperature spans the range of the temperature easy to decarbonize, the temperature is too high, the decarbonization of the refractory material can still be influenced, and the highest baking temperature of 900 ℃ can be controlled to reduce the decarbonization of the refractory material and simultaneously reduce the phenomenon that steel is cooled due to the fact that the temperature of a water gap is too low during casting.
Example 1 and comparative example 1
The method comprises selecting 8-machine 8-flow tundish with left and right sides separated (4 flows on the left and right sides, that is, 4 tundish submerged nozzles on the left and right tundish respectively (Al)2O3quality-C)), under the condition that other process parameters are not changed, the submerged nozzles of the left and right tundish are made of the same manufacturer (such as Vesverver), and the chemical components of refractory materials are close to each other to meet the requirement of Al2O3More than or equal to 50 percent and C more than or equal to 1 percent.
Example 1: the total baking time of the left tundish is required to be 5 hours during the test, the left tundish is firstly baked for about 1 hour, and the temperature of a tundish submerged nozzle is required to be kept at about 100 ℃ within 1 hour; then rapidly heating to 700 ℃, heating at a speed of 30 ℃/min, and keeping the temperature at 700 ℃ for 3 h; then heating to 900 ℃, and preserving the heat for about 1 h;
comparative example 1: the total baking time of the right tundish is required to be 8 hours during the test, the right tundish is firstly baked for about 1 hour, and the temperature of a tundish submerged nozzle is required to be kept at about 100 ℃ within 1 hour; then rapidly heating to 700 ℃, and preserving heat for 6h at 700 ℃; then the temperature is increased to 900 ℃ again, and the temperature is kept for about 1 h.
And (3) controlling the baking of the tundish to ensure that the two final tundishes both pull and cast 10 furnaces and 20 pipes of molten steel, and measuring the depth of a decarburization layer of the refractory material and large-size inclusions in the steel.
The decarburization depth measuring method comprises the following steps: and taking the submerged nozzle after drawing casting, preparing a sample, then placing the sample under a scanning electron microscope to measure the decarburization depth, and taking the average value of the decarburization depths of 4 nozzles as the decarburization depth value under corresponding test parameters.
After the drawing and casting are finished, the decarburization depth of 4 tundish submerged nozzles on the left side is detected to be about 1.2 mm; the decarburization depth of the 4 tundish submerged nozzles on the right side is about 2.6 mm. The number of large-size calcium aluminate inclusions in a steel product is detected by contrast, 176 samples are detected for the steel produced by the tundish on the left side, 9 large-size calcium aluminates (more than or equal to 13 mu m) are found, and 0.0511 large-size calcium aluminate inclusions exist in each sample on average; the steel produced by the tundish on the right side is tested by 184 samples, and 19 large-size calcium aluminates (more than or equal to 13 mu m) are found, and on average, 0.1033 large-size calcium aluminate inclusions exist in each sample.
Example 2 and comparative example 2
The method comprises selecting 8-machine 8-flow tundish (4 flows in the left and right sides, namely 4 tundish submerged nozzles in the left and right tundish), and using the same manufacturer (such as Vesverver) for the submerged nozzles of the left and right tundish under the condition of no change of other process parameters, wherein the chemical components of refractory are close to each other to satisfy the requirement of Al2O3More than or equal to 50 percent and C more than or equal to 1 percent.
Example 2: the total baking time of the tundish on the left side is required to be 3 hours during the test, the tundish is firstly baked for 1 hour, and the submerged nozzle temperature of the tundish is required to be kept at about 100 ℃ in the 1 hour; then rapidly heating to 700 ℃, and preserving heat for 1h at 700 ℃; then heating to 900 ℃, and preserving the heat for about 1 h;
comparative example 2: the total baking time of the right tundish is required to be 8 hours during the test, the right tundish is firstly baked for about 1 hour, and the temperature of a tundish submerged nozzle is required to be kept at about 100 ℃ within 1 hour; then rapidly heating to 700 ℃, and preserving heat for 6h at 700 ℃; then the temperature is increased to 900 ℃ again, and the temperature is kept for about 1 h.
And (3) controlling the baking of the tundish to ensure that the two final tundishes both pull and cast 10 furnaces and 20 pipes of molten steel, and measuring the depth of a decarburization layer of the refractory material and large-size inclusions in the steel.
After the drawing and casting are finished, the decarburization depth of 4 tundish submerged nozzles on the left side is detected to be about 0.2 mm; the decarburization depth of the 4 tundish submerged nozzles on the right side is about 2.5 mm. The number of large-size calcium aluminate inclusions in a steel product is detected by contrast, 173 samples of the steel produced by the tundish on the left side are detected, 2 large-size calcium aluminates (more than or equal to 13 mu m) are found, and 0.0116 large-size calcium aluminate inclusions exist in each sample on average; 189 samples of the steel produced by the right-side tundish are detected, 20 large-size calcium aluminates (more than or equal to 13 mu m) are found, and 0.1058 large-size calcium aluminate inclusions are found in each sample on average.
Example 3 and comparative example 3
The method comprises selecting 8-machine 8-flow tundish (4 flows in the left and right sides, namely 4 tundish submerged nozzles in the left and right tundish), and using the same manufacturer (such as Vesverver) for the submerged nozzles of the left and right tundish under the condition of no change of other process parameters, wherein the chemical components of refractory are close to each other to satisfy the requirement of Al2O3More than or equal to 50 percent and C more than or equal to 1 percent.
Example 3: the total baking time of the left tundish is required to be 4 hours during the test, the left tundish is firstly baked for about 1 hour, and the temperature of a tundish submerged nozzle is required to be kept at about 100 ℃ within 1 hour; then rapidly heating to 700 ℃, and preserving heat for 2h at 700 ℃; then heating to 900 ℃, and preserving the heat for about 1 h;
comparative example 3: the total baking time of the right tundish is required to be 10 hours during the test, the right tundish is firstly baked for about 1 hour, and the temperature of a tundish submerged nozzle is required to be kept at about 100 ℃ within 1 hour; then rapidly heating to 700 ℃, and preserving heat for 8h at 700 ℃; then the temperature is increased to 900 ℃ again, and the temperature is kept for about 1 h. And (3) controlling the baking of the tundish to ensure that the two final tundishes both pull and cast 10 furnaces and 20 pipes of molten steel, and measuring the depth of a decarburization layer of the refractory material and large-size inclusions in the steel.
After the drawing and casting are finished, the decarburization depth of 4 tundish submerged nozzles on the left side is detected to be about 0.9 mm; the decarburization depth of the 4 tundish submerged nozzles on the right side is about 3.7 mm. The number of large-size calcium aluminate inclusions in a steel product is detected by contrast, 179 samples are detected for the steel produced by the tundish on the left side, and 6 large-size calcium aluminates (more than or equal to 13 mu m) are found, and 0.0335 large-size calcium aluminate inclusions exist in each sample on average; 188 samples were tested on the steel produced by the tundish on the right side, and 27 large-size calcium aluminates (not less than 13 μm) were found, and 0.1436 large-size calcium aluminate inclusions in each sample on average.
Comparative example 3': the total baking time of the right tundish is required to be 4 hours during the test, the right tundish is firstly baked for about 1 hour, and the temperature of a tundish submerged nozzle is required to be kept at about 100 ℃ within 1 hour; then rapidly heating to 700 ℃, wherein the heating speed is 30 ℃/min, and keeping the temperature at 700 ℃ for 2 h; then the temperature is raised to 1200 ℃, the temperature raising speed is 30 ℃/min, and the temperature is kept for about 1 h.
After the completion of the drawing casting of comparative example 3', the decarburization depth of the right 4 tundish submerged nozzles was measured to be about 1.0 mm. The number of large-size calcium aluminate inclusions in the steel product is detected by comparison, 173 samples are detected for the steel produced by the tundish on the right side, 8 large-size calcium aluminates (not less than 13 mu m) are found, and 0.0462 large-size calcium aluminate inclusions are found in each sample on average.
Example 4 and comparative example 4
The method comprises selecting 8-machine 8-flow tundish (4 flows in the left and right sides, namely 4 tundish submerged nozzles in the left and right tundish), and using the same manufacturer (such as Vesverver) for the submerged nozzles of the left and right tundish under the condition of no change of other process parameters, wherein the chemical components of refractory are close to each other to satisfy the requirement of Al2O3More than or equal to 50 percent and C more than or equal to 1 percent.
Example 4: the total baking time of the left tundish is required to be 3 hours during the test, the left tundish is firstly baked for about 1.5 hours, and the temperature of a tundish submerged nozzle is required to be kept at about 100 ℃ within the 1.5 hours; then rapidly heating to 700 ℃, and preserving heat for 0.5h at 700 ℃; then heating to 900 ℃, and preserving the heat for about 1 h;
comparative example 4: the total baking time of the right tundish is required to be 8 hours during the test, the right tundish is firstly baked for about 1.5 hours, and the temperature of a tundish submerged nozzle is required to be kept at about 100 ℃ within the 1.5 hours; then rapidly heating to 700 ℃, and preserving the heat for 5.5 hours at 700 ℃; then the temperature is increased to 900 ℃ again, and the temperature is kept for about 1 h. And (3) controlling the baking of the tundish to ensure that the two final tundishes both pull and cast 10 furnaces and 20 pipes of molten steel, and measuring the depth of a decarburization layer of the refractory material and large-size inclusions in the steel.
After the drawing and casting are finished, the decarburization depth of 4 tundish submerged nozzles on the left side is detected to be about 0.1 mm; the decarburization depth of the 4 tundish submerged nozzles on the right side is about 2.4 mm. The quantity of large-size calcium aluminate inclusions in a steel product is detected by contrast, 180 samples are detected for the steel produced by the tundish on the left side, 1 large-size calcium aluminate (more than or equal to 13 mu m) is found, and 0.0056 large-size calcium aluminate inclusions exist in each sample on average; the steel produced by the tundish on the right side is tested by 181 samples, and 16 large-size calcium aluminates (more than or equal to 13 mu m) are found, and each sample has 0.0884 large-size calcium aluminate inclusions on average.
TABLE 1 summary of data for examples and comparative examples
Claims (3)
1. A method for reducing large-size calcium aluminate inclusions in steel is characterized by comprising the following steps: the method comprises the following steps:
(1) controlling Al by baking system2O3The decarburization depth of the refractory material of the C-quality submerged nozzle is reduced to ensure that the decarburization depth of the inner wall of the refractory material is less than or equal to 1.5mm, and large-size calcium aluminate inclusions in steel are reduced;
the specific baking system is as follows: selection of Al2O3The submerged nozzle of the C-quality tundish is required to be baked for 3-5 hours in total, the submerged nozzle is firstly baked for 1-1.5 hours, and the temperature of the submerged nozzle of the tundish is required to be kept at 100 ℃ within 1-1.5 hours; then rapidly heating to 600-800 ℃, and preserving heat for 0.5-3 h; after heat preservation, the temperature is raised to 900 ℃, and heat preservation is carried out for 1h at 900 ℃;
(2) the main component of the refractory lining is Al2O3And C, by mass percentage, wherein Al2O3≥50%、C≥1%。
2. A method for reducing large-size calcium aluminate inclusions in steel according to claim 1, wherein: the size of the large-size calcium aluminate inclusion is more than or equal to 13 mu m.
3. A method for reducing large-size calcium aluminate inclusions in steel according to claim 2, wherein: the large-size calcium aluminate inclusion contains CaO (wt%)/Al in an amount of 0.56-0.562O3(wt%)≤3。
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| JPS54126631A (en) * | 1978-03-27 | 1979-10-02 | Aikoh Co | Dipping nozzle for steel casting |
| JPS58154447A (en) * | 1982-03-10 | 1983-09-13 | Sumitomo Metal Ind Ltd | Method for preventing clogging of immersion nozzle |
| KR20060080251A (en) * | 2002-01-28 | 2006-07-07 | 제이에프이 스틸 가부시키가이샤 | Immersion nozzle for continuous casting |
| CN1170785C (en) * | 2002-10-08 | 2004-10-13 | 胜威高温陶瓷(鞍山)有限公司 | Aluminum-carbon refractory material and its preparation |
| CN1283589C (en) * | 2004-07-28 | 2006-11-08 | 宝山钢铁股份有限公司 | Refractory material in use for continuous casting and usage |
| CN1796028A (en) * | 2004-12-24 | 2006-07-05 | 中钢集团洛阳耐火材料研究院 | Anti sealed immersion nozzle in use for continuous casting specific steel |
| CN101205140A (en) * | 2006-12-23 | 2008-06-25 | 周成德 | High-carbon refractory and method for preparing same |
| CN101906502A (en) * | 2010-08-23 | 2010-12-08 | 首钢总公司 | Calcium treating method for reducing size of D and Ds type of inclusions containing aluminum steel |
| CN102503461B (en) * | 2011-10-21 | 2014-06-18 | 山东东耐高温材料股份有限公司 | Submerged argon blowing nozzle for continuously casting metals and preparation method thereof |
| CN205519630U (en) * | 2016-01-27 | 2016-08-31 | 上海梅山钢铁股份有限公司 | Continuous casting immersion nozzle of aluminium carbon material |
| CN107127332B (en) * | 2016-02-29 | 2018-12-04 | 鞍钢股份有限公司 | A kind of production method preventing wadding stream submersed nozzle |
| CN107999732B (en) * | 2017-11-07 | 2019-10-18 | 河钢股份有限公司承德分公司 | Ultra-low carbon coating tundish builds by laying method |
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