MOLTEN STEEL DENITRIFICATION METHOD AND STEEL PRODUCTION METHOD
20240271235 ยท 2024-08-15
Assignee
Inventors
Cpc classification
International classification
Abstract
A molten steel denitrification method including CaO-and-Al.sub.2O.sub.3-containing slag is formed by adding a metal-Al-containing substance to molten steel to deoxidize and turn the molten steel into Al-containing molten steel and adding a CaO-containing substance to the molten steel, and then an oxygen-containing gas is blown from above the slag to perform a denitrification treatment. T.Math.Fe in the slag after the denitrification treatment is set to 3.0 mass % or lower. It is preferable that, in the denitrification treatment, the oxygen-containing gas be supplied such that a ratio L.sub.s/L.sub.s0 between a thickness L.sub.s0 of the slag and a depth L.sub.s of a depression in the slag resulting from blowing of the oxygen-containing gas becomes 0.9 or lower. The obtained molten steel is cast after its components are adjusted. The method allows an extremely low nitrogen concentration range to be stably reached in a short time.
Claims
1. A molten steel denitrification method in which CaO-and-Al.sub.2O.sub.3-containing slag is formed by a combination of an Al addition step of adding a metal-Al-containing substance to molten steel to deoxidize and turn the molten steel into Al-containing molten steel and a CaO addition step of adding a CaO-containing substance to the molten steel, and then an oxygen-containing gas is blown from above and through the slag to perform a denitrification treatment without using carbide denitrification flux, wherein the Al concentration is adjusted to a predetermined range in the Al addition step, the atmospheric pressure in the furnace during the denitrification process is adjusted to a predetermined range, the mass ratio C/A of CaO to Al.sub.2O.sub.3 is within a predetermined range for the slag composition, and the MgO concentration is within a predetermined range, wherein the molten steel temperature during the denitrification process is adjusted to a predetermined range in consideration of the MgO concentration, wherein T.Math.Fe in the slag after the denitrification treatment is set to 3.0 mass % or lower.
2. The molten steel denitrification method according to claim 1, wherein, in the denitrification treatment, the oxygen-containing gas is supplied such that a ratio L.sub.s/L.sub.s0 between a thickness L.sub.s0 of the slag and a depth L.sub.s of a depression in the slag resulting from blowing of the oxygen-containing gas becomes 0.9 or lower.
3. The molten steel denitrification method according to claim 1, wherein, in the denitrification treatment, the oxygen-containing gas is an O.sub.2 gas diluted with an inert gas other than an N.sub.2 gas.
4. The molten steel denitrification method according to claim 1, wherein, in the Al addition step, an Al concentration [Al] in the molten steel is set to between 0.1 mass % and 1.0 mass %, both inclusive.
5. The molten steel denitrification method according to claim 1, wherein, in the denitrification treatment, surfaces of the Al-containing molten steel and the slag are subjected to a depressurized atmosphere.
6. The molten steel denitrification method according to claim 1, wherein a temperature T.sub.f of the molten steel undergoing the denitrification treatment is increased by 5? C. or more each time an MgO concentration (MgO) in the slag increases by 1.0 mass %, compared to the molten steel temperature during said denitrification process required to reduce the nitrogen concentration in the molten steel to a predetermined value when there is no MgO in the slag.
7. A steel production method wherein molten steel smelted by the molten steel denitrification method according to claim 1 is cast after components are arbitrarily adjusted.
8. The molten steel denitrification method according to claim 2, wherein, in the denitrification treatment, the oxygen-containing gas is an O.sub.2 gas diluted with an inert gas other than an N.sub.2 gas.
9. The molten steel denitrification method according to claim 2, wherein, in the Al addition step, an Al concentration [Al] in the molten steel is set to between 0.1 mass % and 1.0 mass %, both inclusive.
10. The molten steel denitrification method according to claim 3, wherein, in the Al addition step, an Al concentration [Al] in the molten steel is set to between 0.1 mass % and 1.0 mass %, both inclusive.
11. The molten steel denitrification method according to claim 8, wherein, in the Al addition step, an Al concentration [Al] in the molten steel is set to between 0.1 mass % and 1.0 mass %, both inclusive.
12. The molten steel denitrification method according to claim 2, wherein, in the denitrification treatment, surfaces of the Al-containing molten steel and the slag are subjected to a depressurized atmosphere.
13. The molten steel denitrification method according to claim 3, wherein, in the denitrification treatment, surfaces of the Al-containing molten steel and the slag are subjected to a depressurized atmosphere.
14. The molten steel denitrification method according to claim 4, wherein, in the denitrification treatment, surfaces of the Al-containing molten steel and the slag are subjected to a depressurized atmosphere.
15. The molten steel denitrification method according to claim 8, wherein, in the denitrification treatment, surfaces of the Al-containing molten steel and the slag are subjected to a depressurized atmosphere.
16. The molten steel denitrification method according to claim 9, wherein, in the denitrification treatment, surfaces of the Al-containing molten steel and the slag are subjected to a depressurized atmosphere.
17. The molten steel denitrification method according to claim 10, wherein, in the denitrification treatment, surfaces of the Al-containing molten steel and the slag are subjected to a depressurized atmosphere.
18. The molten steel denitrification method according to claim 11, wherein, in the denitrification treatment, surfaces of the Al-containing molten steel and the slag are subjected to a depressurized atmosphere.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0029]
[0030]
[0031]
[0032]
[0033]
[0034]
[0035]
[0036]
DESCRIPTION OF EMBODIMENTS
[0037] Embodiments of the present invention will be specifically described below. The drawings are schematic and may differ from the reality. The following embodiments illustrate a device and a method for embodying the technical idea of the present invention, and are not intended to restrict the configuration to the one described below. Thus, various changes can be made to the technical idea of the present invention within the technical scope described in the claims.
[0038]
[0039] A step of adding a metal-Al-containing substance to the molten steel 3 to deoxidize the molten steel 3 and turn it into Al-containing molten steel (Al addition step) and a step of adding a CaO-containing substance to the molten steel 3 (CaO addition step) may be performed using the alloy addition system 12 or may be performed in a step before entering the vacuum vessel 13. The step of deoxidizing the molten steel 3 (deoxidation step) may be performed separately from the Al addition step. The CaO addition step can be performed at an arbitrary timing. Performing the CaO addition step after the deoxidation step is preferable, because then the temperature rise of the molten steel due to the deoxidation reaction can be used to flux the slag. Performing the CaO addition step after the Al addition step is further preferable, because this can reduce deoxidation failure or variation in the slag composition due to the added Al-containing substance being hindered by the thick slag from reaching the molten steel.
[0040] To form the CaO-and-Al.sub.2O.sub.3-containing slag 4, Al.sub.2O.sub.3 resulting from adding the CaO-containing substance and deoxidizing the molten steel is used. This may be done using, as the CaO-containing substance, for example, calcium aluminate that is a pre-melted or pre-mixed product. As for the slag composition, a higher melting ratio (fluxing ratio) of the slag is more advantageous for the denitrification reaction, and a mass ratio C/A between CaO and Al.sub.2O.sub.3 is preferably within a range of 0.4 to 1.8 and more preferably within a range of 0.7 to 1.7.
[0041] The form of supplying the stirring gas 10 into the molten steel may be, other than the above-described method, for example, a form of injecting it into the molten steel through an injection lance for blowing in an inert gas. Next, preferred embodiments of the present invention will be described in detail along with how they were developed.
First Embodiment
[0042] A first embodiment was devised out of necessity to clearly and quantitatively present conditions advantageous for denitrification, for, even when a test was conducted within the range of the compatible example in Patent Literature 3, denitrification was not stable and the reached nitrogen concentration was not reduced, either. In a small-sized high-frequency vacuum induction melting furnace satisfying the configuration requirements of
[0043] Of the tests described above, in a test in which the T.Math.Fe concentration (T.Math.Fe) in the slag was 15 mass % or higher, it was clearly recognizable with the naked eye that the oxygen gas had penetrated through the slag layer and exposed the surface of the molten steel. By contrast, in a test in which the T.Math.Fe concentration was lower than 15%, clear exposure of the surface of the molten steel was not recognized at any locations including the surface onto which the oxygen gas was blown. Thus, removing nitrogen to a low nitrogen concentration range in accordance with what was described in Patent Literature 3 proved difficult. The result of the study as just described led to the development of the first embodiment, i.e., a molten steel denitrification method in which CaO-and-Al.sub.2O.sub.3-containing slag is formed by a combination of an Al addition step of adding a metal-Al-containing substance to molten steel to deoxidize and turn the molten steel into Al-containing molten steel and a CaO addition step of adding a CaO-containing substance to the molten steel, and then an oxygen-containing gas is blown from above the slag to perform a denitrification treatment, wherein T.Math.Fe in the slag after the denitrification treatment is set to 3.0 mass % or lower. The lower limit of T.Math.Fe in the slag may be 0 mass %. In this Description, [M] represents a state of element M being dissolved and contained in molten steel, and (R) represents a state of a chemical substance R being dissolved and contained in slag. Units are added to express their respective composition ratios.
Second Embodiment
[0044] A second embodiment was found in the course of conducting tests in the aforementioned small-sized high-frequency vacuum induction melting furnace to address the challenge of how to control the T.Math.Fe concentration (T.Math.Fe) in the slag after the denitrification treatment to 3.0 mass % or lower. First, an X-ray diffraction (XRD) analysis was performed on each of slags after the denitrification treatment, respectively obtained in a test in which the oxygen gas clearly penetrated through the slag layer and the nitrogen concentration [N] in the molten steel after the treatment was higher than 35 mass ppm, and a test in which the surface of the molten steel was not exposed during the test and the concentration decreased to 35 mass ppm or lower. As a result, as shown in
[0045] To control the ratio L.sub.s/L.sub.s0 of the slag depression depth, a method of increasing or decreasing the lance height or the gas flow rate, appropriately shaping the nozzle tip of the gas top-blowing lance, and various other methods can be adopted. The present inventors have confirmed that if, for example, the value of L/L.sub.s0 when the lance height is changed and the value of L.sub.s/L.sub.s0 when the gas flow rate is changed are the same, the T.Math.Fe concentrations (T.Math.Fe).sub.f in the slag are equivalent, and that no difference due to the difference in control means occurs. Depending on the scale of the device, the thickness of the slag being treated can decrease for reasons such as part of the slag infiltrating into the refractory or the slag getting involved into the molten steel as the molten steel is stirred. However, the upper limit value of the ratio L.sub.s/L.sub.s0 of the slag depression depth should be adjusted to be lower than 0.9 as appropriate based on this technical idea.
Third Embodiment
[0046] A third embodiment was found in the course of conducting studies to make the present invention applicable also to a facility in which it is difficult to control the T.Math.Fe concentration in the slag through the ratio L/L.sub.s0 of the slag depression depth for some reason, such as ascending and descending of the top-blowing lance being controlled stepwise. Specifically, this embodiment involves reducing the oxygen gas concentration in the oxygen-containing gas. In a test using the aforementioned small-sized high-frequency vacuum induction furnace, a denitrification treatment was performed while an inert gas was supplied through the gas pipe 9 to reduce the oxygen concentration in the gas blown onto the slag from 1.5 mass % (industrial crude Ar level) to 0.1 mass ppm (industrial Ar level). Here, as the inert gas, a gas that does not include nitrogen is used. As a result, as shown in
Fourth Embodiment
[0047] Patent Literature 3 requires an Al concentration [Al] in molten steel of 0.3 mass % to 2 mass % as a concentration needed to increase the ratio of nitrogen distribution between slag and metal, which makes it costly to smelt ordinary steel. A fourth embodiment was found in the course of exploring the possibilities of removing nitrogen with the Al concentration [Al] in the molten steel reduced to an even lower concentration to solve this problem. In the aforementioned small-sized high-frequency vacuum induction melting furnace, a minimum required Al concentration [Al], for reducing the nitrogen [N].sub.f in molten steel to 25 mass ppm was studied. As a result, as shown in
Fifth Embodiment
[0048] A fifth embodiment was found in the course of studying an influence that a reached degree of vacuum P inside the vacuum vessel exerted on the reached nitrogen concentration [N].sub.f. In the aforementioned small-sized high-frequency vacuum induction melting furnace, the reached nitrogen concentration [N].sub.f was studied by performing a denitrification treatment several times at different timings, with the ratio L.sub.s/L.sub.s0 of the slag depression depth set to 0.9 in the case where the gas blown onto the CaO-and-Al.sub.2O.sub.3-containing slag was an oxygen gas and with the ratio L.sub.s/L.sub.s0 of the slag depression depth set to 1.2 in the case of a diluted gas (with an oxygen concentration in the gas 0.1 ppm to 1.5 mass %). As a result, as shown in
Sixth Embodiment
[0049] A sixth embodiment was found in the course of studying an influence of the MgO concentration (MgO) in the CaO-and-Al.sub.2O.sub.3-containing slag. Using the aforementioned small-sized high-frequency vacuum induction melting furnace, a study was conducted on a molten steel temperature T.sub.f that was required to reduce the nitrogen [N].sub.f in the molten steel to 25 mass ppm when the MgO concentration (MgO) in the CaO-and-Al.sub.2O.sub.3-containing slag was changed over a range of 0 mass % to a saturated concentration. As a result, as shown in
(Steel Production Method)
[0050] It is preferable that molten steel smelted by the above-described molten steel denitrification method be cast after additionally it is adjusted to a predetermined composition and form control and floating separation of inclusions are performed as necessary. It is possible to produce high-grade steel which is low-nitrogen steel and of which various components have been adjusted.
Examples
[0051] In the following, examples of the present invention will be described in detail. Using the device having the configuration of
[0052] Table 1 shows the test conditions and the results. Treatments No. 1 to 7 in which the T.Math.Fe concentration (T.Math.Fe) in the slag is sufficiently low produced good results with the N concentration [N].sub.f after the treatment being 35 mass ppm or lower. By contrast, in treatment No. 8 in which T.Math.Fe concentration (T.Math.Fe) in the slag is high, denitrification in same treatment time was insufficient.
TABLE-US-00001 TABLE 1 Slag (TFe)f (C/A)* (MgO) Gas L.sub.S/L.sub.S0 [Al] P Tf [N]i [N]f t No. mass % mass % type mass % 10.sup.5 Pa ? C. massppm massppm min Remarks 1 2.9 0.67 0 Oxygen 0.9 0.08 1.0 1600 50 35 30 Invention Example 2 0.5 1.0 5 Oxygen 0.6 0.9 1.0 1620 50 34 30 Invention Example 3 1.0 1.0 5 Diluted 1.0 0.09 1.0 1624 50 30 30 Invention Example 4 0.5 0.67 10 Oxygen 0.5 0.28 1.0 1600 50 24 30 Invention Example 5 0.8 0.67 10 Oxygen 0.6 0.5 1.0 1645 50 20 30 Invention Example 6 0.5 1.0 10 Oxygen 0.5 0.3 0.04 1600 50 16 30 Invention Example 7 0.9 0.67 10 Diluted 0.9 0.1 0.04 1660 50 13 30 Invention Example 8 29 0.67 0 Oxygen 1.5 0.08 1.0 1600 50 50 30 Comparative Example
INDUSTRIAL APPLICABILITY
[0053] When applied to a steelmaking process of producing molten steel by melting low-carbon scrap or reduced iron in an electric furnace etc., the molten steel denitrification method according to the present invention can stably mass-produce low-nitrogen steel. Thus, this method contributes to reducing CO.sub.2 and is industrially useful.
REFERENCE SIGNS LIST
[0054] 1 Vessel [0055] 2 Refractory [0056] 3 Molten steel [0057] 4 CaO-and-Al.sub.2O.sub.3-containing slag [0058] 5 Gas pipe (oxygen gas) [0059] 6 Gas top-blowing lance [0060] 7 Oxygen-containing gas [0061] 8 Bottom-blowing nozzle [0062] 9 Gas pipe (inert gas) [0063] 10 Stirring inert gas [0064] 11 Exhaust system [0065] 12 Alloy addition system [0066] 13 Vacuum vessel