CN114214481A - A method for reducing nitrogen content in steel - Google Patents
A method for reducing nitrogen content in steel Download PDFInfo
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- CN114214481A CN114214481A CN202111442395.7A CN202111442395A CN114214481A CN 114214481 A CN114214481 A CN 114214481A CN 202111442395 A CN202111442395 A CN 202111442395A CN 114214481 A CN114214481 A CN 114214481A
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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
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/06—Deoxidising, e.g. killing
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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
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/064—Dephosphorising; Desulfurising
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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
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/068—Decarburising
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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
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Abstract
The invention provides a method for reducing nitrogen content in steel, which comprises the steps of mixing scrap steel and molten iron, and smelting to obtain end-point molten steel; carrying out steel tapping deoxidation operation on the smelting molten steel so that the mass fraction of oxygen in the molten steel is more than or equal to 0.01 percent to obtain steel tapping molten steel; carrying out RH refining treatment on the tapping molten steel at the vacuum pressure of 0.067-0.50KPa to obtain RH refined molten steel; and carrying out full-protection pouring on the RH refined molten steel to obtain a plate blank for the steel with low nitrogen content. By adopting the method provided by the invention, the nitrogen content in the slab can be reduced to 26-32ppm, the nitrogen content is low, and meanwhile, the sulfur content is 0.0017-0.0019%, the requirement of high-strength steel is met, and the pouring process is smooth.
Description
Technical Field
The invention belongs to the technical field of steel making, and particularly relates to a method for reducing nitrogen content in steel.
Background
High-strength steel has the advantages of high strength, large weight reduction potential, good formability and the like, and is increasingly used for replacing conventional varieties so as to better meet the development of green, high-efficiency and low-carbon production. The important difficulty in the production of high-strength steel is smelting, especially the element control of molten steel. The control fluctuation of the elements is large, which can result in poor quality of the high-strength steel. In order to improve the strength, high-strength steel generally adopts various alloy elements such as Mn, Ti and the like to increase the strength, under the background, if the nitrogen content of molten steel is higher, TiN precipitates or inclusions are easy to precipitate in the solidification process, when the size of TiN exceeds a certain range, the toughness and plasticity of the high-strength steel are influenced, and in severe cases, the deep drawing performance, the welding performance and the like are even influenced, so researchers adopt various means to remove the nitrogen element in the high-strength steel.
At present, because various alloy elements are added into high-strength steel in component design, based on the consideration of multiple aspects such as desulfurization, more alloy elements, inclusion control and the like, a converter → LF → RH → CC process is generally adopted, the process is longer in working procedure, so that the nitrogen increase in the smelting process is accumulated, the nitrogen content of the produced high-strength steel slab is higher, and the nitrogen cannot be removed in the slab rolling process, so that the plasticity and toughness of the high-strength steel are influenced.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for reducing the nitrogen content in steel, which has lower nitrogen content on the premise of ensuring smooth casting and low sulfur content, so that the steel has good plasticity and toughness.
The invention provides a method for reducing the nitrogen content in steel, which comprises the following steps,
mixing scrap steel and molten iron, and smelting to obtain converter end-point molten steel;
carrying out steel tapping deoxidation operation on the converter end point molten steel so that the mass fraction of oxygen in the molten steel is more than or equal to 0.01% and obtaining steel tapping molten steel;
carrying out RH refining treatment on the tapping molten steel under the vacuum pressure of 0.067-0.50KPa to obtain RH refined molten steel;
and carrying out full-protection pouring on the RH refined molten steel to obtain a plate blank for the steel with low nitrogen content.
Further, the mass fraction of oxygen in the molten steel is 0.01-0.03%.
Further, in the RH refined molten steel, the mass fraction of carbon is 0.02-0.08%, and the mass fraction of oxygen is 0.0010-0.0030%.
Further, the mass fraction of carbon in the molten steel at the end point of the converter is 0.04-0.08%.
Further, the loading amount of the scrap steel is 8-15% of the total loading amount.
Further, oxygen blowing and decarburization are carried out in the smelting process, and pellets are added for slagging; when the oxygen blowing amount is 85-90% of the total oxygen blowing amount, the adding mass of the pellets is 8-15kg/t steel.
Further, when tapping is finished, 2-5kg of lime and 1-3kg/t of slow-release deoxidizer are added to the slag surface of the molten steel for desulfurization.
Furthermore, the service life of the RH dip pipe used for the RH refining treatment is less than or equal to 50 times.
Further, the capacity of the refining furnace for RH refining is 120-300 t.
Further, in the protective pouring process, the volume fraction of oxygen in the atmosphere in the tundish is controlled to be less than or equal to 1%.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the invention provides a method for reducing nitrogen content in steel, wherein oxygen-bearing smelting is adopted in both the processes of steel tapping in a converter smelting molten steel and RH refining to inhibit nitrogen absorption of the molten steel, meanwhile, deep vacuum treatment is adopted in the RH refining to ensure the thermodynamic condition of nitrogen removal of the molten steel, and casting is protected in the continuous casting process to prevent nitrogen increase. By adopting the method provided by the invention, the nitrogen content in the RH refined molten steel is reduced to 26-30ppm, the nitrogen content is low, the sulfur content is 0.0017-0.0019%, the requirement of high-strength steel is met, and the pouring process is smooth.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a process diagram of a method for reducing nitrogen content in steel according to an embodiment of the present invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
It is noted that, in this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions.
In order to solve the technical problems, the embodiment of the invention provides the following general ideas:
the embodiment of the invention provides a method for reducing the nitrogen content in steel, which comprises the following steps,
s1, mixing the scrap steel with molten iron, and smelting to obtain end-point molten steel;
as an implementation mode of the embodiment of the invention, the mass fraction of carbon in the final molten steel is 0.04-0.08%.
The carbon content of the molten steel at the end point of the converter is controlled to be more than or equal to 0.04 percent, so that nitrogen absorption caused by molten steel peroxidation due to too low carbon drawing of the molten steel is avoided. The carbon content in the molten steel at the end point is too high, and the requirement of steel grade is not met; the carbon content in the molten steel is too high to exceed the target carbon content.
As an embodiment of the present invention, the charged amount of the scrap steel is 8 to 15% of the total charged amount.
In the invention, the waste steel and the molten iron are loaded into the converter for smelting, the converter is the most important link for controlling the nitrogen content of the molten steel, and particularly, the nitrogen content of the molten steel is easily increased due to the weakened carbon-oxygen reaction in the later stage of blowing of the converter, so that the loading amount of the waste steel is controlled to be 8-15% of the total loading amount, the heat abundance of the converter is ensured, and the nitrogen absorption of the molten steel due to the over oxidation of the molten steel caused by insufficient heat at the end point of the converter is avoided; on the other hand, the end point temperature of the converter can be ensured, and the problem that the temperature of the steel liquid in the tundish is too low and the pouring cannot be carried out due to the fact that the LF process is removed and the temperature is not raised is avoided. The low converter end point temperature and insufficient heat can be caused by the overlarge loading amount of the scrap steel; the charging amount of the scrap steel is too small, which is not beneficial to cooling and cost control.
As an implementation mode of the embodiment of the invention, oxygen is blown for decarburization in the smelting process, and pellets are added for slagging; when the oxygen blowing amount is 85-90% of the total oxygen blowing amount, the adding mass of the pellets is 8-15kg/t steel.
When oxygen supply is required to be 85-90%, the addition amount of the converter pellets is 8-15kg/t steel, so that the converter pellets have enough slag amount in the later blowing stage, the contact between molten steel and air is reduced, and the nitrogen absorption of the molten steel is reduced; if the addition amount of the pellet ore is too large, the slag amount is possibly too large, and the cost is high; if the addition amount of the pellet ore is too small, the slag amount is insufficient, and the molten steel is exposed, so that the molten steel absorbs nitrogen. The pellet in the invention is alkaline pellet, and the T.Fe content is more than or equal to 65%.
S2, performing steel tapping deoxidation operation on the final-point molten steel to enable the mass fraction of oxygen in the molten steel to be more than or equal to 0.01%, and obtaining steel tapping molten steel;
deoxidizing agent is added in the tapping process for deoxidation, and the deoxidation is semi-deoxidation, so that the molten steel contains oxygen and the molten steel can absorb nitrogen in the tapping process. The deoxidizer in the invention can be ferrosilicon.
As an implementation mode of the embodiment of the invention, the mass fraction of oxygen in the molten steel is 0.01-0.03%.
The oxygen content in the molten steel is too high, so that the inclusion in the steel is more and the cleanliness is low.
As an implementation mode of the embodiment of the invention, when tapping is finished, 2-5kg of lime and 1-3kg/t of slow-release deoxidizer are added to the slag surface of molten steel for desulfurization.
Meanwhile, in order to ensure the accuracy of alloying, after tapping, 2-5kg/t of steel with lime and 1-3kg/t of steel with slow-release deoxidizer are added on the slag surface, so that the desulfurizing effect can be achieved, the balance of Si elements among the slag steel is ensured, and the alloying effect is ensured.
The slow-release deoxidizer is a high-aluminum slow-release deoxidizer, wherein the mass fraction of aluminum is 45-60%, the mass fraction of CaO in the slow-release deoxidizer is 3-5%, the mass fraction of MgO is 3-5%, and SiO is mainly used2Is 3-5% of Al2O3The mass fraction of (A) is 30-46%. In practice, lime is generally a small particle of lime having a particle size of 10-50 mm.
The addition of lime has excessive quality, so that resource waste is caused, and the over-high alkalinity is not beneficial to lime melting and the effect of efficient desulfurization is difficult to achieve; the lime added with too little mass can not play the role of desulfurization.
The slow-release deoxidizer is added with excessive quality, so that resource waste is caused, and the alkalinity is too high to facilitate lime melting, so that the effect of high-efficiency desulfurization is difficult to achieve; (ii) a The slow-release deoxidizer has too low added quality, cannot reduce the FeO content in the slag, and is difficult to ensure the desulfurization effect.
S3, carrying out RH refining treatment on the tapping molten steel under the vacuum pressure of 0.067-0.50KPa to obtain RH refined molten steel;
the invention requires to control the whole RH process to be in a deep vacuum state, thereby guaranteeing the denitrification effect thermodynamically.
In one embodiment of the present invention, in the RH refined molten steel, the mass fraction of carbon is 0.02 to 0.08%, and the mass fraction of oxygen is 0.0010 to 0.0030%.
The steel type smelted in the invention is high-strength steel, and alloy elements such as Mn, Ti and the like need to be added in the smelting process, so that medium-carbon ferromanganese and carbon are added in a matching way, and low-nitrogen ferrotitanium and ferromanganese are added in a matching way, so that nitrogen is prevented from being contained in the alloy and substituted into molten steel, and nitrogen increase in the RH process is avoided.
On the other hand, in order to ensure the alloying effect, in the RH process, decarburization → deoxidation → alloying operation is adopted, in the alloying process, medium carbon ferromanganese is adopted to be matched with C, and other low nitrogen alloys are matched with Mn, so that the aim of controlling the nitrogen content of different alloys is to ensure that the nitrogen content of the alloys is the lowest, and the effect of avoiding RH nitrogen increase is realized. After RH decarburization is finished, deoxidizing agent Al particles are added for deoxidation.
As an embodiment of the invention, the service life of the RH dip pipe used for the RH refining treatment is less than or equal to 50 times.
In the RH process, the balance of denitrification and nitrogen increase exists under the vacuum condition, and the nitrogen source is mainly cracks of the RH dip pipe, so that the service life of the dip pipe is required to be controlled to be less than or equal to 50 times, and the phenomenon that the molten steel absorbs nitrogen due to more cracks caused by overlarge service life of the RH dip pipe is avoided.
And S4, carrying out full-protection pouring on the RH refined molten steel to obtain a slab for the steel with low nitrogen content.
Continuous casting is also a link which is easy to generate nitrogen increase, therefore, the invention requires adopting a full-protection pouring measure, controlling the nitrogen content in the tundish below 3% before casting, controlling the tundish to blow argon in the blowing process and sealing the ladle cover, and realizing the effect of controlling the continuous casting nitrogen increase below 2ppm by the measures.
As an implementation mode of the embodiment of the invention, in the protective pouring process, the volume fraction of oxygen in the atmosphere in the tundish is controlled to be less than or equal to 1%.
As an implementation manner of the embodiment of the invention, the RH furnace used for the RH refining treatment has a capacity of 120-300 tons.
The method for reducing the nitrogen content in steel according to the present invention will be described in detail with reference to examples, comparative examples and experimental data.
Example 1
Embodiment 1 provides a method for reducing nitrogen content in steel, which adopts a process route of 210t converter → RH → continuous casting, and adopts the following smelting process, specifically:
1. and charging the molten iron and the scrap steel into a converter for converter oxygen blowing smelting to obtain converter smelting molten steel. Specifically, the total loading amount is 235t, wherein the loading amount of the scrap steel is 8 percent of the total loading amount, and when oxygen is supplied for 85 percent in the converter smelting process, the adding amount of the converter pellet is 8kg/t steel; the carbon content of the molten steel at the end point of the converter is 0.045%, the oxygen content is 0.04%, and the temperature is 1640 ℃.
2. Tapping the converter smelting molten steel obtained in the step 1 into a steel ladle to obtain tapping molten steel; deoxidizing agent is added in the process of tapping to deoxidize, and alloy is added to carry out alloying. Specifically, Si is deoxidized to ensure that the oxygen content of the tapping molten steel is 150 ppm; when tapping is finished, small-particle lime 2kg/t steel and high-aluminum slow-release deoxidizer 1kg/t steel are added into the slag surface for desulfurization.
3. And conveying the desulfurized molten steel tapping liquid to an RH station for RH vacuum treatment to obtain RH refined molten steel. The main operation sequence of the RH vacuum treatment process is decarburization → deoxidation → alloying; in the alloying process, medium carbon ferromanganese is adopted to prepare C, other low nitrogen alloys are adopted to prepare Mn, meanwhile, the whole RH vacuum treatment process is controlled to be in a deep vacuum state, the vacuum pressure is 0.067kPa, and the using frequency of a dip pipe used in the RH vacuum treatment process is 9 th.
4. And hoisting the RH refined molten steel to a continuous casting process for full-protection casting to obtain a plate blank. In the pouring process, the pouring basket is filled with 2-5Nm3Blowing argon at a flow rate of/min, and arranging a ladle cover on the tundish for sealing.
The nitrogen content in the tundish before casting is 1.5 percent.
Example 2
Embodiment 1 provides a method for reducing nitrogen content in steel, which adopts a 300t converter → RH → continuous casting process route, and adopts the following smelting process, specifically:
1. and charging the molten iron and the scrap steel into a converter for converter oxygen blowing smelting to obtain converter smelting molten steel. Specifically, the total loading amount is 328t, wherein the loading amount of the scrap steel is 11% of the total loading amount, and when oxygen is supplied for 87% in the converter smelting process, the adding amount of the converter pellets is 11kg/t steel; the carbon content of the molten steel at the end point of the converter is 0.04%, the oxygen content is 0.04%, and the temperature is 1638 ℃.
2. Tapping the converter smelting molten steel obtained in the step 1 into a steel ladle to obtain tapping molten steel; deoxidizing agent is added in the process of tapping to deoxidize, and alloy is added to carry out alloying. Specifically, Si is deoxidized to ensure that the oxygen content of the molten steel is 110 ppm; when tapping is finished, adding 3kg/t of small-particle lime steel and 2kg/t of high-aluminum slow-release deoxidizer into the slag surface for desulfurization.
3. And conveying the desulfurized molten steel tapping liquid to an RH station for RH vacuum treatment to obtain RH refined molten steel. The main operation sequence of the RH vacuum treatment process is decarburization → deoxidation → alloying; in the alloying process, medium carbon ferromanganese is adopted to prepare C, other low nitrogen alloys are adopted to prepare Mn, meanwhile, the whole RH vacuum treatment process is controlled to be in a deep vacuum state, the vacuum pressure is 0.067kPa, and the using frequency of a dip pipe used in the RH vacuum treatment process is 25 th.
4. And hoisting the RH refined molten steel to a continuous casting process for full-protection casting to obtain a plate blank. And in the pouring process, the tundish is blown with argon to protect pouring, and the tundish is provided with a ladle cover for sealing.
The nitrogen content in the tundish before casting is 1 percent.
Example 3
Embodiment 1 provides a method for reducing nitrogen content in steel, which adopts a process route of 120t converter → RH → continuous casting, and adopts the following smelting process, specifically:
1. and charging the molten iron and the scrap steel into a converter for converter oxygen blowing smelting to obtain converter smelting molten steel. Specifically, the total loading amount is 135t, wherein the loading amount of the scrap steel is 15% of the total loading amount, and when oxygen is supplied for 88% in the converter smelting process, the adding amount of the converter pellets is 15kg/t steel; the carbon content of the molten steel at the end point of the converter is 0.06%, the oxygen content is 0.035%, and the temperature is 1662 ℃.
2. Tapping the converter smelting molten steel obtained in the step 1 into a steel ladle to obtain tapping molten steel; deoxidizing agent is added in the process of tapping to deoxidize, and alloy is added to carry out alloying. Specifically, Si is deoxidized to ensure that the oxygen content of the tapping molten steel is 150 ppm; when tapping is finished, adding 5kg/t of small-particle lime steel and 3kg/t of high-aluminum slow-release deoxidizer into the slag surface for desulfurization.
3. And conveying the desulfurized molten steel tapping liquid to an RH station for RH vacuum treatment to obtain RH refined molten steel. The main operation sequence of the RH vacuum treatment process is decarburization → deoxidation → alloying; in the alloying process, medium carbon ferromanganese is adopted to prepare C, other low nitrogen alloys are adopted to prepare Mn, meanwhile, the whole RH vacuum treatment process is controlled to be in a deep vacuum state, the vacuum pressure is 0.12kPa, and the using frequency of a dip pipe used in the RH vacuum treatment process is 49 times.
4. And hoisting the RH refined molten steel to a continuous casting process for full-protection casting to obtain a plate blank. And in the pouring process, the tundish is blown with argon to protect pouring, and the tundish is provided with a ladle cover for sealing. The nitrogen content in the tundish before casting is 2.5 percent.
Comparative example 1
Comparative example 1 provides a method for smelting high-strength steel, which adopts a process route of converter → LF → RH → continuous casting, and adopts the following smelting process, specifically:
1. and (4) after the smelting of the converter is finished, carrying out tapping operation, and adding a deoxidizing agent to deoxidize in the tapping process so that the oxygen content in the tapping molten steel is 0.0030%.
2. Carrying out LF refining on the tapping molten steel, and carrying out heating and desulfurization to obtain LF refined molten steel; the oxygen content in the LF refined molten steel is 0.0028%, and the carbon content is 0.04%.
3. Carrying out RH vacuum treatment on the LF refined molten steel to obtain RH refined molten steel;
4. and pouring the RH refined molten steel to obtain a plate blank.
TABLE 1
As can be seen from the data in Table 1, the method for reducing the nitrogen content in the steel provided by the embodiment of the invention can reduce the nitrogen content in the RH refined molten steel to 26-30ppm, simultaneously has the sulfur content of 0.0017-1.0019%, and has a smooth pouring process. Comparative example 1 provides a conventional method for smelting high-strength steel, which makes the nitrogen content in the slab 42ppm lower than that provided in the inventive example, because the nitrogen content in the molten steel is very high during tapping and LF because the molten steel is highly stirred; and the sulfur content in the molten steel in the tundish provided in comparative example 1 was 0.0017%, which is at the same level as in examples 1 to 3 of the present invention. From the above analysis, the method for reducing the nitrogen content in the steel provided by the embodiment of the invention has lower nitrogen content on the premise that the slab has low sulfur content, and the high-strength steel can have better plasticity and toughness after the slab is rolled.
The invention provides a method for reducing nitrogen content in steel, wherein oxygen-bearing smelting is adopted in both the processes of steel tapping in a converter smelting molten steel and RH refining to inhibit nitrogen absorption of the molten steel, meanwhile, deep vacuum treatment is adopted in the RH refining to ensure the thermodynamic condition of nitrogen removal of the molten steel, and casting is protected in the continuous casting process to prevent nitrogen increase. By adopting the method provided by the invention, the nitrogen content of the molten steel in the tundish can be reduced to 26-32ppm, the nitrogen content is low, and the sulfur content is 0.0017-0.0019%, so that the requirement of high-strength steel is met, and the pouring process is smooth.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
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| CN115820971A (en) * | 2022-07-22 | 2023-03-21 | 首钢京唐钢铁联合有限责任公司 | Control method for low nitrogen content of low-carbon steel |
| CN116145019A (en) * | 2023-03-30 | 2023-05-23 | 宝武集团鄂城钢铁有限公司 | A smelting method for producing flaw detection steel without RH process |
| CN118272719A (en) * | 2024-04-28 | 2024-07-02 | 北京首钢股份有限公司 | Smelting method of clean steel and clean steel |
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