CN115094299A - Steelmaking production process of aluminum-containing cold forging steel - Google Patents
Steelmaking production process of aluminum-containing cold forging steel Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 238
- 239000010959 steel Substances 0.000 title claims abstract description 238
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 180
- 238000009628 steelmaking Methods 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 238000010273 cold forging Methods 0.000 title claims abstract description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000002893 slag Substances 0.000 claims abstract description 81
- 238000010079 rubber tapping Methods 0.000 claims abstract description 44
- 229910052786 argon Inorganic materials 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000007664 blowing Methods 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 29
- 238000007670 refining Methods 0.000 claims abstract description 28
- 229910000616 Ferromanganese Inorganic materials 0.000 claims abstract description 26
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 238000003723 Smelting Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000005275 alloying Methods 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- -1 aluminum-manganese-iron Chemical compound 0.000 claims abstract description 7
- 230000000903 blocking effect Effects 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 238000009749 continuous casting Methods 0.000 claims description 45
- 239000011575 calcium Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 19
- 229910052791 calcium Inorganic materials 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 19
- WNQQFQRHFNVNSP-UHFFFAOYSA-N [Ca].[Fe] Chemical compound [Ca].[Fe] WNQQFQRHFNVNSP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 claims description 8
- 208000004434 Calcinosis Diseases 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 230000002308 calcification Effects 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 229910000640 Fe alloy Inorganic materials 0.000 claims 1
- 239000005997 Calcium carbide Substances 0.000 abstract description 5
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 abstract description 5
- 238000009847 ladle furnace Methods 0.000 description 40
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000024121 nodulation Effects 0.000 description 5
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000010436 fluorite Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910001208 Crucible steel Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
- C22C33/06—Making ferrous alloys by melting using master alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/16—Controlling or regulating processes or operations
- B22D11/18—Controlling or regulating processes or operations for pouring
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0006—Adding metallic additives
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0056—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires
-
- 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
- C21C7/0075—Treating in a ladle furnace, e.g. up-/reheating of molten steel within the ladle
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/06—Deoxidising, e.g. killing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/064—Dephosphorising; Desulfurising
-
- 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
- C21C7/076—Use of slags or fluxes as treating agents
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Carbon Steel Or Casting Steel Manufacturing (AREA)
Abstract
The invention provides a steel-making production process of aluminum-containing cold heading steel, which relates to the technical field of metallurgical steel-making and comprises the following steps: s1: in the smelting of a molten iron converter, the phosphorus content at the end point is controlled, the slag blocking plug of the converter blocks slag and steel are tapped, and the slag discharge amount of the converter is controlled; s2: adding refined synthetic slag into a molten steel tank before tapping of the converter, and controlling the component content of the refined synthetic slag; s3: in the converter tapping process, medium carbon ferromanganese and aluminum ferromanganese are adopted for deoxidation alloying, the addition amount is adjusted according to the components and the single-furnace tapping amount, and the manganese element content of the molten steel entering the CAS station and the acid molten aluminum content of the molten steel entering the CAS station are controlled; s4: after molten steel enters a CAS argon blowing station, determining the quantity of aluminum wires to be added according to the content of acid-melted aluminum entering the station; the aluminum-containing cold forging steel produced by the method has stable components, and because the aluminum-manganese-iron dosage is adjusted by tapping, the burning loss of acid-melted aluminum in the refining process is avoided, the aluminum-manganese-iron deoxidization is realized, the silicon element and the acid-melted aluminum content in the aluminum-containing cold forging steel can be stably controlled, the calcium carbide is avoided, and the carbon emission is reduced.
Description
Technical Field
The invention relates to the technical field of metallurgical steelmaking, in particular to a steelmaking production process of aluminum-containing cold heading steel.
Background
The aluminum-containing cold heading steel is subjected to one-time or multiple-time impact loading at room temperature, is widely used for producing standard parts such as screws, pins, nuts and the like, and the cold heading process can save raw materials and reduce cost, improve the tensile strength of a workpiece and improve the performance through cold work hardening;
the steelmaking production process of the aluminum-containing cold heading steel is a key technology for aluminum-containing cold heading steel production, and a common deoxidizer for the aluminum-containing cold heading steel steelmaking production comprises the following steps: silicon-aluminum-barium, aluminum-manganese-iron, calcium carbide and the like; the molten aluminum is obtained by feeding aluminum wires or aluminum particles into molten steel;
in the prior art, most steel mills adopt: the method comprises the following steps of producing aluminum cold forging steel by a steelmaking process flow of blast furnace molten iron-converter-LF furnace refining-continuous casting, wherein a silicon-containing deoxidizer is used for deoxidizing during converter tapping (mainly comprising silicon-aluminum-barium deoxidizing alloy), so that the silicon content of molten steel cannot be stably controlled at a lower level; calcium carbide is used for deoxidation in the converter tapping process, fluorite is used for slagging in the refining process, and the environment is not protected; in the existing aluminum-containing cold forging steel making process, most converter steel tapping deoxidation is insufficient, a large amount of aluminum wires are required to be fed for deoxidation in the refining process, the acid-melted aluminum content entering a CAS station and exiting the CAS station has no clear control range requirement, the operation difficulty of quick white slag making and stable acid-melted aluminum content control of an LF (ladle furnace) is increased, and the high-efficiency S, O and quick white slag making operation of refining of the LF is not facilitated; meanwhile, the refining process has the defects of large aluminum wire consumption, molten steel pollution, easy generation of nozzle nodulation during continuous casting, difficulty in realizing multi-furnace continuous casting, inconvenience for production of aluminum-containing cold forging steel, stable quality and increase of production cost, so the invention provides a steelmaking production process of aluminum-containing cold forging steel to solve the problems in the prior art.
Disclosure of Invention
Aiming at the problems, the invention provides a steelmaking production process of aluminum-containing cold heading steel, which can stably control the contents of silicon element and acid-melted aluminum in the aluminum-containing cold heading steel and reduce carbon emission.
In order to realize the purpose of the invention, the invention is realized by the following technical scheme: a steelmaking production process of aluminum-containing cold forging steel comprises the following steps:
s1: in the smelting of a molten iron converter, the phosphorus content at the end point is controlled, the slag blocking plug of the converter blocks slag and steel are tapped, and the slag discharging amount of the converter is controlled;
s2: adding refined synthetic slag into a molten steel tank before tapping of the converter, and controlling the component content of the refined synthetic slag;
s3: in the converter tapping process, medium carbon ferromanganese and aluminum ferromanganese are adopted for deoxidation alloying, the addition amount is adjusted according to the components and the single-furnace tapping amount, and the manganese element content of the molten steel entering the CAS station and the acid molten aluminum content of the molten steel entering the CAS station are controlled;
s4: after molten steel enters a CAS argon blowing station, determining the quantity of aluminum wires to be added according to the content of acid-melted aluminum entering the station, controlling the content of acid-dissolved aluminum in the molten steel exiting the CAS station, blowing argon after the aluminum wires are fed, and then exiting the station to a lifting LF furnace for refining;
s5: the LF furnace adopts the operation of adding aluminum particles to manufacture white slag, the adding amount of the aluminum particles and the white slag time are controlled, and the argon blowing flow is adjusted to control the content of acid-melted aluminum in the molten steel of the manufactured LF furnace to be more than or equal to 0.035%;
s6: carrying out calcification treatment according to the content of acid-melted aluminum in molten steel before the molten steel is out of the station, controlling the addition amount of the iron-calcium wire according to the calcium-aluminum ratio of the molten steel out of the station, carrying out soft argon blowing after the iron-calcium wire is fed, and adding a molten steel covering agent when the molten steel is out of the station;
s7: adding pure calcium lines between the impact zone and each flow of the continuous casting tundish to react to generate low-melting-point 12CaO 7Al 2 O 3 ；
S8: the molten steel is poured from a molten steel tank to a continuous casting crystallizer in a full protection mode, the molten steel tank is protected in an argon sealing mode, and a slag wall and a molten steel composite heat preservation agent are used in a continuous casting tundish, so that the oxygen content in the continuous casting tundish is reduced to the minimum.
The further improvement lies in that: in the S1, the phosphorus content at the smelting end point of the converter is controlled to be less than or equal to 0.015 percent, the slag blocking plug of the converter blocks slag and steel is tapped, and the slag discharging amount of the converter is controlled to be less than or equal to 50 mm.
The further improvement lies in that: in the S2, the refined synthetic slag comprises the following components in percentage by weight: CaO content of 45% -53%, Al 2 O 3 39-44% of SiO 2 The content is less than or equal to 6 percent, and the content of MgO is less than or equal to 5 percent.
The further improvement lies in that: in the S3, medium carbon ferromanganese and aluminum ferromanganese are deoxidized and alloyed in the converter tapping process, the adding amount is adjusted according to the components and the single-furnace tapping amount, the content of manganese element in molten steel entering a CAS station is controlled to be within the range of 0.25-0.4%, the content of acid molten aluminum in molten steel entering the CAS station is controlled to be within the range of 0.02-0.05%, wherein in the carbon ferromanganese, the content of manganese element is more than or equal to 70%, the content of carbon element is less than 4%, and the content of silicon element is less than or equal to 2%; in the aluminum-manganese-iron, the content of aluminum element is more than or equal to 42 percent, the content of manganese element is more than or equal to 15 percent, the content of carbon element is less than or equal to 1 percent, and the content of silicon element is less than or equal to 2 percent.
The further improvement lies in that: in the S4, after molten steel enters a CAS argon blowing station, the quantity of aluminum wires added is determined according to the acid-soluble aluminum content of incoming molten steel, the acid-soluble aluminum content of the molten steel at the CAS station is controlled to be within the range of 0.055% -0.075%, the argon blowing time is controlled to be more than 2min after the aluminum wire feeding is finished, and then the molten steel is taken out of the CAS station to be lifted to an LF furnace for refining, wherein the aluminum element content in the aluminum wire is more than or equal to 99%.
The further improvement lies in that: in the S5, the LF furnace adopts the operation of adding aluminum particles to make white slag, the adding amount of the aluminum particles is controlled to be 50-150kg, the white slag time is controlled to be more than 20min, and the argon blowing flow is adjusted to control the content of acid-melted aluminum in molten steel of the LF furnace to be more than or equal to 0.035%, wherein the content of aluminum elements in the aluminum particles is more than or equal to 99%.
The further improvement lies in that: in the S6, calcification treatment is carried out before leaving the station according to the content of acid-melted aluminum in molten steel, the adding amount of iron-calcium wires is controlled according to the calcium-aluminum ratio of the molten steel leaving the station within the range of 0.10-0.15, and feeding is finishedControlling the soft argon gas blowing time to be more than or equal to 10min after the iron-calcium line, controlling the final slag alkalinity of the LF furnace to be 3-4.5, adding a molten steel covering agent to prevent the molten steel from reacting with oxygen in the air after the molten steel leaves a station, covering a large tank by using a steel ladle, wherein the calcium content is more than or equal to 40 percent when the molten steel is fed into the calcium line, the carbon content is 2-15 percent and the SiO content is 2-15 percent in the molten steel covering agent 2 The content of the compound is more than or equal to 65 percent.
The further improvement lies in that: in the S7, pure calcium lines are added between the impact area of the continuous casting tundish and each flow to oxidize Al generated in the continuous casting tundish 2 O 3 Reacts with Ca in molten steel to generate 12CaO 7Al with low melting point 2 O 3 Wherein, the content of calcium element is more than or equal to 97 percent when the calcium is added into the pure calcium line.
The further improvement lies in that: in S8, the molten steel is poured from the molten steel tank to the continuous casting crystallizer in a full protection mode, the long nozzle of the molten steel tank and the bowl opening of the lower nozzle of the tundish are protected by argon seal, the continuous casting tundish uses a slag wall and a molten steel composite heat preservation agent, the oxygen content of the continuous casting tundish is reduced to the minimum, the superheat degree of the molten steel of a normal continuous casting furnace is controlled to be less than or equal to 35 ℃, the drawing speed is controlled to be less than or equal to 3.6m/mim, wherein the CaO content in the molten steel composite heat preservation agent is greater than or equal to 10%, Al content in the molten steel is greater than or equal to 3.6m/mim 2 O 3 The content is more than or equal to 10 percent and SiO 2 The content is more than or equal to 30 percent and the content of carbon element is more than or equal to 7 percent.
The invention has the beneficial effects that:
1. the aluminum-containing cold forging steel produced by the method has stable components, and because the dosage of aluminum, manganese and iron is adjusted during tapping, the burning loss of acid-melted aluminum in the refining process is avoided, the aluminum, manganese and iron are deoxidized, the contents of silicon element and acid-melted aluminum in the aluminum-containing cold forging steel can be stably controlled, calcium carbide is avoided, and the carbon emission is reduced.
2. According to the invention, the refining synthetic slag is added in the converter tapping, so that the refining process of the LF furnace is promoted to quickly produce white slag, the content of acid-melted aluminum in steel billets and steel products meets the standard requirement, the quick production of the white slag in the LF furnace is beneficial to the removal of S and O of molten steel, the use of fluorite for slagging is avoided in the whole process, and no environmental pollution is caused.
3. The method has the advantages that the production process of the aluminum-containing cold forging steel is stable, the aluminum-containing cold forging steel is taken out of the LF furnace, calcium-aluminum ratio is controlled, the generation of high-melting-point aluminum oxidation in the molten steel is avoided, the floating of the high-melting-point aluminum oxidation is promoted by enough soft blowing time, and secondary oxidation of the molten steel is effectively avoided by matching with protective pouring measures such as steel ladle capping, molten steel composite heat preservation agent, water gap argon sealing and the like, the generation of water gap nodulation is avoided, the fluidity and the pourability of the molten steel are improved, and the production of the cast steel is stabilized.
4. The method has strong operability in producing the aluminum-containing cold forging steel, uses carbon ferromanganese for alloying in converter tapping, uses aluminum ferromanganese for deoxidation, and determines the content standard of acid-melted aluminum entering the CAS station and exiting the CAS station, thereby laying a foundation for the stable control of the content of the acid-melted aluminum in the refining operation of the LF furnace, and avoiding the influence of the operation of feeding aluminum wires or adding aluminum particles in the middle and later stages of the refining process of the molten steel on the quality and the production stability of the aluminum-containing cold forging steel.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
In order to further understand the present invention, the following detailed description will be made with reference to the following examples, which are only used for explaining the present invention and are not to be construed as limiting the scope of the present invention.
Example one
According to the illustration in FIG. 1, the embodiment provides a steel-making production process of aluminum-containing cold heading steel, which comprises the following steps:
s1: in the smelting of a molten iron converter, the phosphorus content at the end point is controlled, the slag blocking plug of the converter blocks slag and steel are tapped, and the slag discharge amount of the converter is controlled;
s2: adding refined synthetic slag into a molten steel tank before tapping of the converter, and controlling the component content of the refined synthetic slag;
s3: in the converter tapping process, medium carbon ferromanganese and aluminum ferromanganese are adopted for deoxidation alloying, the addition amount is adjusted according to the components and the single-furnace tapping amount, and the manganese element content of the molten steel entering the CAS station and the acid molten aluminum content of the molten steel entering the CAS station are controlled;
s4: after molten steel enters a CAS argon blowing station, determining the quantity of aluminum wires to be added according to the content of acid-melted aluminum entering the station, controlling the content of acid-dissolved aluminum in the molten steel exiting the CAS station, blowing argon after the aluminum wires are fed, and then exiting the station to a lifting LF furnace for refining;
s5: the LF furnace adopts the operation of adding aluminum particles to manufacture white slag, the adding amount of the aluminum particles and the white slag time are controlled, and the argon blowing flow is adjusted to control the content of acid-melted aluminum in the molten steel of the manufactured LF furnace to be more than or equal to 0.035%;
s6: carrying out calcification treatment according to the content of acid-melted aluminum in molten steel before the molten steel is out of the station, controlling the addition amount of the iron-calcium wire according to the calcium-aluminum ratio of the molten steel out of the station, carrying out soft argon blowing after the iron-calcium wire is fed, and adding a molten steel covering agent when the molten steel is out of the station;
s7: adding pure calcium lines in the impact zone of continuous casting ladle and between each flow to react to generate low-melting 12CaO 7Al 2 O 3 ；
S8: the molten steel is poured from a molten steel tank to a continuous casting crystallizer in a full protection mode, the molten steel tank is protected in an argon sealing mode, and a slag wall and a molten steel composite heat preservation agent are used in a continuous casting tundish, so that the oxygen content in the continuous casting tundish is reduced to the minimum.
Example two
The embodiment provides a steelmaking production process of aluminum-containing cold heading steel, which comprises the following process flows of: molten iron → converter smelting → converter slag stopping plug slag stopping tapping → CAS station wire feeding and argon blowing control → LF furnace white slag manufacturing → molten steel full-process protective pouring and continuous casting.
The phosphorus content at the smelting end point of the converter is controlled to be less than or equal to 0.015 percent, the converter slag stopping plug stops slag and steel, and the slag discharging amount of the converter is controlled to be less than or equal to 50 mm. The requirements of the molten steel tank are as follows: the steel ladle of steel grade with Si more than 0.30% in major repair, middle repair and upper furnace smelting cannot be used for smelting cold heading steel; the edge and the bottom of the molten steel tank are free of cold steel and cold slag, sand drainage operation is performed by adopting drainage sand, and the water feeding opening of the molten steel tank is automatically drained by 100%.
400kg of refined synthetic slag is added into a molten steel tank before tapping of the converter, so that the later LF furnace process can be facilitated to quickly produce white slag. The CaO content of the refined synthetic slag is required to be 45 to 53 percent, and Al is required to be 2 O 3 39-44% of SiO 2 The content is less than or equal to 6 percent, and the content of MgO is less than or equal to 5 percent.
The medium carbon ferromanganese and aluminum ferromanganese are adopted for deoxidation alloying in the converter tapping process, the adding amount is controlled according to the components and the single-furnace tapping amount tapping, the manganese element content of the molten steel entering the CAS station is ensured to be within the range of 0.25-0.4%, and the acid-melted aluminum content of the molten steel entering the CAS station is ensured to be within the range of 0.02-0.05%. The manganese content in the medium-carbon ferromanganese is required to be more than or equal to 70 percent, the carbon content is less than 4 percent, and the silicon content is less than or equal to 2 percent; the content of aluminum, manganese, iron and aluminum is more than or equal to 42 percent, the content of manganese is more than or equal to 15 percent, the content of carbon is less than or equal to 1 percent, and the content of silicon is less than or equal to 2 percent.
After molten steel enters a CAS argon blowing station, the quantity of aluminum wires added is determined according to the content of acid-soluble aluminum entering the CAS station, the content of acid-soluble aluminum in the molten steel exiting the CAS station is ensured to be in the range of 0.055% -0.075%, the argon blowing time is ensured to be more than 2 minutes after the aluminum wires are fed, and the molten steel exits the CAS station and is conveyed to a lifting LF furnace for refining. The aluminum element content of the aluminum wire is required to be more than or equal to 99 percent.
The LF furnace adopts the operation of adding aluminum particles to manufacture white slag, the adding amount of the aluminum particles is controlled according to 50-150kg, the white slag time is ensured to be more than 20 minutes, the argon blowing flow is adjusted, the molten steel oxidation caused by the violent stirring of an argon column is avoided, and the content of acid-melted aluminum in the molten steel discharged from the LF furnace is ensured to be more than or equal to 0.035%. The aluminum content of the aluminum particles is required to be more than or equal to 99 percent.
Carrying out calcification treatment according to the content of acid-melting aluminum in molten steel before leaving the station, controlling the addition amount of the iron-calcium wire according to the calcium-aluminum ratio of the molten steel leaving the station in the range of 0.10-0.15, and ensuring that the time of soft argon gas blowing is not less than 10 minutes after feeding the iron-calcium wire. And controlling the alkalinity of the final slag of the LF furnace according to the range of 3-4.5. Molten steel covering agent is added when the molten steel is discharged from the station to avoid the reaction of the molten steel and oxygen in the air, and a large tank is covered by a steel ladle. The calcium element content of the fed calcium line is required to be more than or equal to 40 percent. The carbon content of the molten steel covering agent is required to be 2-15 percent, and the SiO content is required to be 2 The content of the compound is more than or equal to 65 percent.
Because the molten steel in the ladle of the casting furnace inevitably has secondary oxidation, the impact area and the flows of the continuous casting tundish adopt a pure calcium adding line accounting for 20 meters, so that Al generated by oxidation in the continuous casting tundish 2 O 3 Reacts with Ca in the molten steel to generate low-melting-point 12 CaO.7 Al 2 O 3 The method avoids the nodulation of the pouring-on water blocking nozzle and also avoids the transition of adopting other non-aluminum steel types for the pouring-on first furnace. The content of calcium element in the added pure calcium line is required to be more than or equal to 97 percent.
The molten steel is poured from a molten steel tank to a continuous casting crystallizer in a full protection mode, a long nozzle of the molten steel tank and a bowl opening of a lower nozzle of a tundish are protected by argon sealing, and a slag wall and a molten steel composite heat insulating agent are used in the continuous casting tundish to ensure that the oxygen content in the continuous casting tundish is reduced to the minimum. The molten steel composite heat-insulating agent requires that the CaO content is more than or equal to 10 percent and Al 2 O 3 The content is more than or equal to 10 percent, and SiO is 2 The content is more than or equal to 30 percent, and the content of carbon element is more than or equal to 7 percent.
The superheat degree of the molten steel in the normal continuous casting furnace is controlled according to the temperature of less than or equal to 35 ℃, and the pulling speed is controlled according to the speed of less than or equal to 3.6 m/mim.
Verification example:
an example of steel production with SWRCH6A is as follows:
the molten iron condition is as follows: the temperature of molten iron is 1323 ℃, the components of the molten iron, C: 4.13 percent; si: 0.46 percent; mn: 0.26 percent; p: 0.162 percent; s; 0.021%.
Loading conditions were as follows: 107.4t of molten iron and 17.2t of scrap steel, and the total weight is 124.6 t.
The composition and temperature of molten steel at the end point of the converter are as follows: determining a shooting sublance matched with a smelting end point, and tapping by pouring steel, wherein the temperature of molten steel is as follows: 1603 ℃, molten steel tapping ingredients, C: 0.038%; si: 0.0016 percent; mn: 0.073%; p: 0.0112%; s; 0.018%, and final oxygen content in molten steel 822 ppm.
Adding alloy in tapping: the steel tapping amount is 117.6t, 540kg of aluminum ferromanganese, 300kg of medium carbon ferromanganese and 400kg of synthetic slag are added in the steel tapping, and the slag discharging amount in the steel tapping is less than 50 mm.
Entering CAS station composition, temperature conditions: temperature in CAS station 1578 ℃, composition in CAS station, C: 0.042 percent; si: 0.017 percent; mn: 0.36 percent; p: 0.013%; s; 0.019 percent, and the content of acid-melted aluminum entering the CAS station is 0.038 percent, which meets the standard of 0.02 to 0.04 percent.
In CAS feed case and at station time control: the aluminum wire was fed 160 meters at the CAS station for 10 minutes at the CAS station.
Composition and temperature conditions of the outgoing CAS station: exit CAS station temperature 1558 ℃, entry CAS station composition, C: 0.052 percent; si: 0.046 percent; mn: 0.37 percent; p: 0.014%; s; 0.018 percent, and the content of acid-melted aluminum at the CAS station is 0.058 percent, which meets the standard of 0.055 percent to 0.075 percent.
And (3) LF furnace charging and power transmission operation: the station-entering temperature of the molten steel is 1549 ℃, the lime is 800kg for the first time, the synthetic slag is 100kg, the power is transmitted for slagging time for 5 minutes, and 80kg of aluminum particles are added in the power transmission process; 300kg of lime is added for the second time, 100kg of synthetic slag is added, power transmission is carried out for 8 minutes, 100kg of lime is added for the third time, power transmission is carried out for 6 minutes, the total time of the three power transmission is 19 minutes, 500 meters of iron-calcium wire are fed after the temperature measurement is finished after the third power transmission, soft blowing is carried out, the argon flow is controlled, the molten steel is prevented from rolling or the molten steel liquid level is prevented from being exposed in the air, secondary oxidation is avoided, temperature measurement sampling and station exit are carried out after 12 minutes of soft blowing, 5-10 packages (10 kg/package) of molten steel composite heat insulating agent are added before the station exit, and the temperature of the molten steel station exit is 1577 ℃.
In-station sampling and out-station sampling component results of the LF furnace: sampling numbers of the three times of power transmission and the feeding calcium wire after soft blowing are respectively L1, L2, L3 and L4, and the results of the components and the temperature are as follows:
LF slag sample results: the serial number of the slag sample after the first power transmission is the first slag sample, the serial number of the slag sample before the station exit is the second slag sample, and the result is as follows:
protection of pouring conditions: and a molten steel tank capping device, a molten steel tank argon blowing long nozzle and a continuous casting tundish argon blowing lower nozzle are adopted, and argon blowing is normal.
Adopting 5-machine 5-flow 155mm square billet continuous casting, after a molten steel tank is poured, the temperature and the flow drawing speed of a continuous casting tundish are as follows:
continuous casting blank components and low-power results: the test results of the components of the continuous casting blank after sampling, cutting and powder drilling are as follows: c: 0.059%; si: 0.053 percent; mn: 0.38 percent; p: 0.011 percent; s; 0.004 percent, and the content of acid-melted aluminum is 0.033 percent, which meets the internal control standard of more than or equal to 0.03 percent. Sampling a continuous casting tundish to perform pinhole oxygen and nitrogen detection, wherein the test result is as follows: o content 25ppm, N content 46 ppm. In the casting process, a group of 10 blocks with low power are respectively taken at the early stage and the middle and later stages of casting, and the results are as follows: low power meeting the requirements
SWRCH6A low fold results:
comparative example:
unlike the two patents with patent numbers of CN103469050A and CN113215498A, the present patent is characterized in that the converter tapping does not use Fe-Si auxiliary material and low-Si pre-melted slag, and the molten steel silicon is stably controlled at a lower level.
Different from two patents with patent numbers of CN103469050A and CN113215498A respectively, this patent is characterized in that the converter tapping and the refining process do not use the carbide as the deoxidant, and the LF refining furnace does not use fluorite as the slagging constituent, satisfies low carbon environmental protection requirement.
Unlike the two patents with patent numbers CN103469050A and CN 113215498A. The carbon ferromanganese alloying is used in the definite converter tapping of this patent, deoxidization with aluminium ferromanganese, and control aluminium ferromanganese addition, it is clear that the molten steel acid melting aluminium content standard of advancing CAS station is in 0.02% -0.05% within range, and converter tapping deoxidation effect can be guaranteed to this operation, can alleviate LF refining process control acid melting aluminium burden again, does benefit to LF stove refining process and LF stove refining terminal acid melting aluminium content control.
The method is different from the technological processes of patent Nos. CN103469050A, CN113215498A and CN113718159A, clearly specifies that the tapping of the converter does not directly enter the LF furnace, and adopts the technological process of molten iron → smelting of the converter → slag stopping and tapping of the converter slag stopping and plug → CAS station wire feeding and argon blowing control → white slag manufacturing of the LF furnace → whole-process protection casting and continuous casting of the molten steel, and the technological process of the patent is different from the technological process of patent No. CN 112251661A.
Different from two patents with patent numbers of CN103469050A and CN113215498A respectively, the CAS aluminum wire argon blowing operation is adopted in the method, the control standard of the content of acid-melted aluminum in the CAS station is determined to be 0.055-0.075%, and a foundation is laid for the operation of quickly manufacturing white slag and stably controlling the content of acid-melted aluminum in the LF furnace. And the control standard of the content of acid-soluble aluminum in the LF refining furnace is more than or equal to 0.035 percent, which is inconsistent with the control standards of the two patents.
Different from two patents with patent numbers of CN103469050A and CN113215498A, the calcium treatment is carried out on the molten steel before the LF refining furnace is discharged, the feeding amount of an iron-calcium wire is flexibly controlled according to the content of molten aluminum in molten steel acid melting, the ratio of calcium to aluminum in the molten steel of the LF refining furnace is definitely 0.10-0.15, and Al generated by oxidizing the molten aluminum in the molten steel acid melting is enabled to be 2 O 3 12CaO 7Al with a low melting point is generated as much as possible 2 O 3 And the fluidity of the molten steel is improved.
Different from two patents with patent numbers of CN103469050A and CN113215498A, the patent specifically requires the use of a molten steel tank cover to reduce the water gap nodulation caused by the secondary oxidation of molten steel in the hoisting and pouring processes of the molten steel tank. After the molten steel tank is started to pour, pure calcium lines are added in the impact area of the continuous casting tundish and among all streams to improve the fluidity of the molten steel, and the continuous casting tundish adopts a molten steel compound heat-preserving agent to preserve heat and avoid secondary oxidation of the molten steel.
Different from two patents with patent numbers of CN103469050A and CN113215498A respectively, when this patent is definitely cast by continuous casting, the long mouth of a river of molten steel jar is sealed with blowing argon to the mouth of a lower mouth of a river bowl of well package, realizes the protection pouring.
Different from patents with patent numbers of CN103469050A, CN113215498A, CN113718159A and CN112251661A, the superheat degree of molten steel of a normal continuous casting furnace is controlled according to the temperature of less than or equal to 35 ℃, and the upper limit of the pulling speed can reach 3.6 m/min.
The aluminum-containing cold forging steel produced by the method has stable components, and because the dosage of aluminum, manganese and iron is adjusted during tapping, the burning loss of acid-melted aluminum in the refining process is avoided, the aluminum, manganese and iron are deoxidized, the contents of silicon element and acid-melted aluminum in the aluminum-containing cold forging steel can be stably controlled, calcium carbide is avoided being used, and the carbon emission is reduced; and the refined synthetic slag is added into the converter tapping, so that the refining process of the LF furnace is promoted to quickly produce white slag, the content of acid-melted aluminum of steel billets and steel products meets the standard requirement, the quick production of the white slag in the LF furnace is beneficial to the removal of S and O of molten steel, the use of fluorite for slagging is avoided, and the environmental pollution is avoided.
The production process of the aluminum-containing cold forging steel is stable, the aluminum-containing cold forging steel is taken out of an LF furnace, calcium-aluminum ratio is controlled to be 0.10-0.15, oxidation of high-melting-point aluminum in molten steel is avoided, floating of the high-melting-point aluminum is promoted by enough soft blowing time, and secondary oxidation of the molten steel is effectively avoided by matching protective pouring measures such as steel ladle capping, molten steel composite heat preservation agent, water gap argon sealing and the like, water gap nodulation is avoided, fluidity and pourability of the molten steel are improved, and cast steel production is stabilized.
The method has strong operability in producing the aluminum-containing cold heading steel, the steel is alloyed by carbon ferromanganese during the converter tapping, the aluminum ferromanganese is used for deoxidation, the content of acid-melted aluminum is controlled during the tapping operation, the standard of the content of acid-melted aluminum entering the CAS station and exiting the CAS station is determined, the content of acid-melted aluminum (0.02-0.05%) in the CAS station is higher, the foundation is laid for the stable control of the content of acid-melted aluminum during the refining operation of the LF furnace, and the influence of the later-stage aluminum wire feeding or aluminum particle adding operation of the molten steel in the refining process on the quality and the production stability of the aluminum-containing cold heading steel is avoided.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The aluminum-containing cold forging steel steelmaking production process is characterized by comprising the following steps of:
s1: in the smelting of a molten iron converter, the phosphorus content at the end point is controlled, the slag blocking plug of the converter blocks slag and steel are tapped, and the slag discharging amount of the converter is controlled;
s2: adding refined synthetic slag into a molten steel tank before tapping of the converter, and controlling the component content of the refined synthetic slag;
s3: in the converter tapping process, medium carbon ferromanganese and aluminum ferromanganese are adopted for deoxidation alloying, the addition amount is adjusted according to the components and the single-furnace tapping amount, and the manganese element content of the molten steel entering the CAS station and the acid molten aluminum content of the molten steel entering the CAS station are controlled;
s4: after molten steel enters a CAS argon blowing station, determining the quantity of aluminum wires to be added according to the content of acid-melted aluminum entering the station, controlling the content of acid-dissolved aluminum in the molten steel exiting the CAS station, blowing argon after the aluminum wires are fed, and then exiting the station to a lifting LF furnace for refining;
s5: the LF furnace adopts the operation of adding aluminum particles to manufacture white slag, the adding amount of the aluminum particles and the white slag time are controlled, and the argon blowing flow is adjusted to control the content of acid-melted aluminum in the molten steel of the manufactured LF furnace to be more than or equal to 0.035%;
s6: carrying out calcification treatment according to the content of acid-melting aluminum in molten steel before the molten steel is discharged, controlling the addition of iron calcium wires according to the calcium-aluminum ratio of the discharged molten steel, carrying out soft argon blowing after the iron calcium wires are fed, and adding a molten steel covering agent when the molten steel is discharged;
s7: adding pure calcium lines between the impact zone and each flow of the continuous casting tundish to react to generate low-melting-point 12CaO 7Al 2 O 3 ；
S8: the molten steel is poured from a molten steel tank to a continuous casting crystallizer in a full protection mode, the molten steel tank is protected in an argon sealing mode, and a slag wall and a molten steel composite heat preservation agent are used in a continuous casting tundish, so that the oxygen content in the continuous casting tundish is reduced to the minimum.
2. The aluminum-containing cold heading steel steelmaking process according to claim 1, wherein the aluminum-containing cold heading steel steelmaking process comprises the following steps: in the S1, the phosphorus content at the smelting end point of the converter is controlled to be less than or equal to 0.015 percent, the slag blocking plug of the converter blocks slag and steel is tapped, and the slag discharging amount of the converter is controlled to be less than or equal to 50 mm.
3. The aluminum-containing cold heading steel steelmaking process according to claim 2, wherein the aluminum-containing cold heading steel steelmaking process comprises the following steps: in the S2, the refined synthetic slag comprises the following components in percentage by weight: CaO content of 45% -53%, Al 2 O 3 39-44% of SiO 2 The content is less than or equal to 6 percent, and the content of MgO is less than or equal to 5 percent.
4. The aluminum-containing cold heading steel steelmaking process according to claim 3, wherein the aluminum-containing cold heading steel steelmaking process comprises the following steps: in the S3, medium carbon ferromanganese and aluminum ferromanganese are adopted for deoxidation alloying in the converter tapping process, the adding amount is adjusted according to the components and the single-furnace tapping amount, the content of manganese element in the molten steel entering the CAS station is controlled to be within the range of 0.25-0.4%, and the content of molten acid-melted aluminum in the molten steel entering the CAS station is controlled to be within the range of 0.02-0.05%, wherein in the carbon ferromanganese, the content of manganese element is more than or equal to 70%, the content of carbon element is less than 4%, and the content of silicon element is less than or equal to 2%; in the aluminum-manganese-iron alloy, the content of aluminum element is more than or equal to 42 percent, the content of manganese element is more than or equal to 15 percent, the content of carbon element is less than or equal to 1 percent, and the content of silicon element is less than or equal to 2 percent.
5. The aluminum-containing cold heading steel steelmaking process according to claim 4, wherein the aluminum-containing cold heading steel steelmaking process comprises the following steps: in the S4, after molten steel enters a CAS argon blowing station, the quantity of aluminum wires added is determined according to the acid-soluble aluminum content of incoming molten steel, the acid-soluble aluminum content of the molten steel at the CAS station is controlled to be within the range of 0.055% -0.075%, the argon blowing time is controlled to be more than 2min after the aluminum wire feeding is finished, and then the molten steel is taken out of the CAS station to be lifted to an LF furnace for refining, wherein the aluminum element content in the aluminum wire is more than or equal to 99%.
6. The aluminum-containing cold heading steel steelmaking process according to claim 5, wherein the aluminum-containing cold heading steel steelmaking process comprises the following steps: in the S5, the LF furnace adopts the operation of adding aluminum particles to make white slag, the adding amount of the aluminum particles is controlled to be 50-150kg, the white slag time is controlled to be more than 20min, and the argon blowing flow is adjusted to control the content of acid-melted aluminum in molten steel of the LF furnace to be more than or equal to 0.035%, wherein the content of aluminum elements in the aluminum particles is more than or equal to 99%.
7. The aluminum-containing cold heading steel steelmaking process according to claim 6, wherein the aluminum-containing cold heading steel steelmaking process comprises the following steps: in the step S6, calcification treatment is carried out before leaving the station according to the acid-melted aluminum content in molten steel, the adding amount of an iron-calcium line is controlled according to the calcium-aluminum ratio of the molten steel leaving the station in the range of 0.10-0.15, the soft argon gas blowing time is controlled to be more than or equal to 10min after the iron-calcium line is fed, the final slag alkalinity of the LF furnace is controlled to be 3-4.5, a molten steel covering agent is added after leaving the station to prevent the molten steel from reacting with oxygen in the air, and a large tank adopts the method ofCovering the steel ladle, wherein the steel ladle is fed into a calcium line, the content of calcium element is more than or equal to 40 percent, and the content of carbon element in the molten steel covering agent is 2 to 15 percent, SiO 2 The content of the compound is more than or equal to 65 percent.
8. The aluminum-containing cold heading steel steelmaking process according to claim 7, wherein the aluminum-containing cold heading steel steelmaking process comprises the following steps: in the S7, pure calcium lines are added between the impact area of the continuous casting tundish and each flow to oxidize Al generated in the continuous casting tundish 2 O 3 Reacts with Ca in the molten steel to generate low-melting-point 12 CaO.7 Al 2 O 3 Wherein, the content of calcium element is more than or equal to 97 percent when the calcium is added into the pure calcium line.
9. The aluminum-containing cold heading steel steelmaking process according to claim 8, wherein the aluminum-containing cold heading steel steelmaking process comprises the following steps: in S8, the molten steel is poured from the molten steel tank to the continuous casting crystallizer in a full protection mode, the long nozzle of the molten steel tank and the bowl opening of the lower nozzle of the tundish are protected by argon seal, the continuous casting tundish uses a slag wall and a molten steel composite heat preservation agent, the oxygen content of the continuous casting tundish is reduced to the minimum, the superheat degree of the molten steel of a normal continuous casting furnace is controlled to be less than or equal to 35 ℃, the drawing speed is controlled to be less than or equal to 3.6m/mim, wherein the CaO content in the molten steel composite heat preservation agent is greater than or equal to 10%, Al content in the molten steel is greater than or equal to 3.6m/mim 2 O 3 The content is more than or equal to 10 percent and SiO 2 The content is more than or equal to 30 percent, and the content of carbon element is more than or equal to 7 percent.
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| CN115747614A (en) * | 2022-11-17 | 2023-03-07 | 唐山瑞丰钢铁（集团）有限公司 | Production method of steel for tinned substrate |
| CN118600149A (en) * | 2024-08-09 | 2024-09-06 | 山西建龙实业有限公司 | Production method of small-section aluminum-containing rectangular blank slag washing and straightening process |
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Application publication date: 20220923 |