CN113088624A - Preparation method of low-inclusion aluminum killed steel - Google Patents
Preparation method of low-inclusion aluminum killed steel Download PDFInfo
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- CN113088624A CN113088624A CN202110219515.0A CN202110219515A CN113088624A CN 113088624 A CN113088624 A CN 113088624A CN 202110219515 A CN202110219515 A CN 202110219515A CN 113088624 A CN113088624 A CN 113088624A
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- 229910000655 Killed steel Inorganic materials 0.000 title claims abstract description 78
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 69
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000011777 magnesium Substances 0.000 claims abstract description 189
- 239000010959 steel Substances 0.000 claims abstract description 185
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 182
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 84
- 239000000956 alloy Substances 0.000 claims abstract description 84
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 83
- 238000000034 method Methods 0.000 claims abstract description 81
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 73
- 238000011282 treatment Methods 0.000 claims abstract description 72
- 238000003723 Smelting Methods 0.000 claims abstract description 21
- 229910018505 Ni—Mg Inorganic materials 0.000 claims abstract description 13
- 229910003023 Mg-Al Inorganic materials 0.000 claims abstract description 12
- 238000005266 casting Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 239000002893 slag Substances 0.000 claims description 21
- 238000007664 blowing Methods 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 230000001681 protective effect Effects 0.000 claims description 13
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 238000005275 alloying Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 31
- 239000000126 substance Substances 0.000 abstract description 7
- 230000008018 melting Effects 0.000 abstract description 6
- 238000002844 melting Methods 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- 230000004048 modification Effects 0.000 description 22
- 238000012986 modification Methods 0.000 description 22
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000011575 calcium Substances 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 230000002411 adverse Effects 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 238000009749 continuous casting Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000009628 steelmaking Methods 0.000 description 7
- 238000009849 vacuum degassing Methods 0.000 description 7
- 229910018134 Al-Mg Inorganic materials 0.000 description 6
- 229910018467 Al—Mg Inorganic materials 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 238000000265 homogenisation Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 238000009489 vacuum treatment Methods 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000010587 phase diagram Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 238000012840 feeding operation Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 229910003112 MgO-Al2O3 Inorganic materials 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007619 statistical method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910007981 Si-Mg Inorganic materials 0.000 description 2
- 229910008316 Si—Mg Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000004925 denaturation Methods 0.000 description 2
- 230000036425 denaturation Effects 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910019089 Mg-Fe Inorganic materials 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000024121 nodulation Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- 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
- C21C7/04—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
- C21C7/10—Handling in a vacuum
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Abstract
The invention particularly relates to a preparation method of low-inclusion aluminum killed steel, belonging to the technical field of steel smelting, and the method comprises the following steps: smelting and continuously casting molten aluminum killed steel to obtain aluminum killed steel; the method comprises the following steps of smelting aluminum killed steel molten steel, and performing magnesium treatment on the aluminum killed steel molten steel, wherein the magnesium treatment comprises the step of adding magnesium-containing alloy into the aluminum killed steel molten steel; the method solves the problem of safe Mg addition by changing the addition form of Mg, overcoming the characteristics of low melting point, small density, high vapor pressure, active chemical property and the like of Mg elements, adopting a method of increasing the melting point and the density and reducing the vapor pressure and the chemical activity, and realizing the safe Mg addition by adopting an intermediate alloy form of Ni-Mg, Mg-Al and the like.
Description
Technical Field
The invention belongs to the technical field of steel smelting, and particularly relates to a preparation method of low-inclusion aluminum killed steel.
Background
Al killed steel is adopted in the steel making process as the name implies, and more than 95% of low alloy steel in the current industrial production is the Al killed steel. A large amount of Al can be generated due to aluminum deoxidation in the production process of aluminum killed steel2O3Inclusion of Al2O3The inclusions are easy to aggregate into clusters and grow, and the mechanical property, the corrosion property and the fatigue property of the steel can be seriously damaged if the inclusions are not removed. Therefore, the modification treatment technology of the inclusions is commonly adopted for Al in industrial production2O3Inclusion modification treatment for reducing large-size Al2O3The size and type of inclusions, thereby improving the overall properties of the steel.
Taking production and smelting of domestic and foreign pipeline steel as an example, the high-cleanness pipeline steel is generally smelted by adopting a process flow of molten iron pretreatment → converter smelting → external refining → slab continuous casting. The specific production method of the steel comprises the following steps: smelting → LF → RH (VD) refining → continuous casting → heating → rolling → water cooling after rolling → finished product. In the aspect of controlling the quality of the steelmaking process, LF + RH (VD) vacuum treatment is adopted, the Ca treatment process is adopted for almost 100 percent of the denaturation treatment of the inclusions in the molten steel, and the Ca treatment can effectively improve the nodulation of a water gap and Al in the steel production2O3The large-scale inclusion removal problem of the denaturation treatment, so that the Ca treatment is widely applied to the smelting production of pipeline steel.
It was found that only liquid phase inclusions with a diameter of more than 25 μm could be removed by flotation, and that the influence of these 15-25 μm inclusions remaining in the molten steel on the steel quality is very detrimental, even if a small fraction of 15-25 μm inclusions is still present in the molten steel after calcium treatment, and even larger calcium aluminate inclusions are found in Ca treated aluminium killed steel, which inclusions cause serious steel quality problems. The method is particularly unfavorable for pipeline steel, particularly acid-resistant pipeline steel and submarine pipeline steel in a corrosive environment, and in addition, inclusions with the diameter of more than 15 mu m are easy to cause hydrogen-induced cracking and hydrogen bubbling of a steel plate, so that the service quality safety of the pipeline steel is seriously threatened.
And Mg oxide is used in pipeline steel for high heat input welding and improving the toughness of a heat affected zone. At present, molten steel Mg treatment is mainly concentrated on ship plate steel and pipeline steel, and is in a test research stage, and few reports are given on industrial batch Mg treatment; the invention of China patent application CN 106399633A relates to a process for treating liquid magnesium in ship plate steel, which adopts Mg-Al core-spun alloy wires to carry out Mg treatment after LF (RH), the feeding position is the position opposite to the two air bricks of a steel ladle and at the radius position from 1/3 to 1/2 of the center of the steel ladle, the wire feeding speed is 2.5 to 4.0 m.s < -1 >, and the soft blowing is more than or equal to 12min after the wire feeding; the Chinese patent application CN102181802A discloses a preparation method of easily-welded high-strength-toughness X80G pipeline steel treated by magnesium, and the laboratory vacuum induction furnace adopts magnesium treatment to obtain the high-strength-toughness X80 pipeline steel, but the technical process is not reported.
Disclosure of Invention
The applicant finds in the course of the invention that: mg can reduce the size of large-particle-size inclusions in the aspect of modifying the inclusions in steel, so that magnesium treatment is carried out on molten steel when the preparation rate is high, and the technical bias is overcome. After Mg treatment, small, hard and spinel oxides are mostly formed in the steel, which oxides are not deformed during rolling. This oxide is much smaller than that of steel which is usually treated with Ca. In Mg-treated steels, solid MgO. Al is formed2O3Spinel, which is not in the form of clusters but randomly distributed in the steel. Although in Mg-treated steels a large amount of small (< 3 μm) oxides precipitate, such small oxide inclusions have hardly any adverse effect on the mechanical properties of the steel. The edges of the steel treated with Mg, which are made of small spinel oxides, are almost all rounded, which is in contrast to Al with sharp corners2O3The inclusions are different. Such spinelsThe oxide can neither initiate the formation of voids nor act like ordinary Al2O3Inclusions act as a source of stress. Therefore, the pair of inclusions present in the Mg-treated steel is H2Both HIC and SSCC properties of S are better than those of Ca treatment.
Meanwhile, the applicant finds that when magnesium is treated on molten steel, the safety problem of explosion can be caused by directly adding Mg no matter in an RH or VD process, and in addition, the Mg has low density and can be on the surface of the molten steel when being added; mg has a low boiling point, is gasified before being added, and is difficult to dissolve in molten steel.
In view of the above problems, the present invention has been made in order to provide a method of producing a low inclusion aluminum killed steel which overcomes or at least partially solves the above problems.
The embodiment of the invention provides a preparation method of low-inclusion aluminum killed steel, which comprises the following steps:
smelting and continuously casting molten aluminum killed steel to obtain aluminum killed steel;
the method comprises the following steps of smelting aluminum killed steel molten steel, and carrying out magnesium treatment on the aluminum killed steel molten steel, wherein the magnesium treatment comprises adding magnesium-containing alloy into the aluminum killed steel molten steel.
Optionally, the magnesium-containing alloy includes at least one of a Ni-Mg alloy and a Mg-Al alloy.
Optionally, the Ni-Mg alloy comprises, by weight: ni 70-90% and Mg 10-30%.
Optionally, the Mg-Al alloy comprises, by weight: al 40-50%, Mg 10-15%, and Fe in balance.
Optionally, the manner of adding the magnesium-containing alloy into the molten aluminum killed steel includes a feeding method, and the feeding method specifically includes: and putting the magnesium-containing alloy into the molten aluminum-killed steel in a protective gas atmosphere, wherein the pressure of the protective gas atmosphere is as follows: 40-100KPa, and the granularity of the magnesium-containing alloy is less than or equal to 30 mm.
Optionally, the mode that magnesium-containing alloy is added to molten aluminum killed steel includes a wire feeding method, the wire feeding method specifically includes: feeding the aluminum killed steel molten steel into a magnesium-containing alloy core-spun yarn, wherein the granularity of the magnesium-containing alloy is 1-3 mm.
Optionally, the amount of the wire feeding of the magnesium-containing alloy cored wire is 0.0002% -0.0018% of the molten aluminum killed steel by weight.
Optionally, the wire feeding depth of the magnesium-containing alloy cored wire is 0.6-0.8 time of the depth of molten steel.
Optionally, the wire feeding speed of the magnesium-containing alloy cored wire is 3m/s-6 m/s.
Optionally, after wire feeding is finished, soft argon blowing is carried out on the molten aluminum killed steel, and the time for soft argon blowing is 3-8 min.
Optionally, the magnesium treatment time is as follows: after molten steel of the aluminum killed steel is subjected to slag deoxidation, molten steel sulfur reduction and molten steel alloying fine adjustment operation.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the preparation method of the low-inclusion aluminum killed steel provided by the embodiment of the invention comprises the following steps: smelting and continuously casting molten aluminum killed steel to obtain aluminum killed steel; the method comprises the following steps of smelting aluminum killed steel molten steel, and performing magnesium treatment on the aluminum killed steel molten steel, wherein the magnesium treatment comprises the step of adding magnesium-containing alloy into the aluminum killed steel molten steel; the method solves the problem of safe Mg addition by changing the addition form of Mg, overcoming the characteristics of low melting point, small density, high vapor pressure, active chemical property and the like of Mg elements, adopting a method of increasing the melting point and the density and reducing the vapor pressure and the chemical activity, and realizing the safe Mg addition by adopting an intermediate alloy form of Ni-Mg, Mg-Al and the like.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
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 flow chart of a method provided by an embodiment of the present invention;
FIG. 2 is an elevation view of a thread feeding method provided by an embodiment of the present invention;
FIG. 3 is a top plan view of a thread feeding method provided by an embodiment of the present invention;
FIG. 4 is a schematic view of the inside of molten steel according to an embodiment of the present invention;
FIG. 5 shows conventional Al of aluminum killed steel provided in comparative example 1 of the present invention2O3Schematic illustration of inclusions;
FIG. 6 is a schematic view of inclusions of an aluminum killed steel after magnesium treatment provided in example 1 of the present invention;
FIG. 7 is a ternary phase diagram of inclusions in treated steel with a magnesium addition of 0.0002% according to example 3 of the present invention;
FIG. 8 is a ternary phase diagram of inclusions in treated steel with a magnesium addition of 0.0004% according to example 3 of the present invention;
FIG. 9 is a ternary phase diagram of inclusions in steel treated with Mg in an amount of 0.0018% according to example 3 of the present invention;
FIG. 10 is a ternary phase diagram of inclusions in a treated steel with a magnesium addition of 0.0022% according to example 3 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.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
in China, the research on the molten steel Mg treatment technology is mostly used in the experimental and basic theory research stages, and the popularization and application of the industrial technology are not reported in a public way. The invention provides an aluminum killed steel Mg treatment process technology based on an aluminum killed steel production process. Comprises a set of process technologies such as raw material preparation, adding station, method and corresponding process treatment applied in the Mg treatment industry. The technology can realize safe and efficient industrial batch application of the Mg treatment process under atmosphere or vacuum negative pressure under different working conditions in production. The aim of fine control of the series of high-quality aluminum killed steel on the inclusion is met.
According to an exemplary embodiment of the present invention, there is provided a method of manufacturing a low-inclusion aluminum killed steel, the method including:
smelting and continuously casting molten aluminum killed steel to obtain aluminum killed steel;
the method comprises the following steps of smelting aluminum killed steel molten steel, and carrying out magnesium treatment on the aluminum killed steel molten steel, wherein the magnesium treatment comprises adding magnesium-containing alloy into the aluminum killed steel molten steel.
As an alternative embodiment, the magnesium-containing alloy includes at least one of a Ni-Mg alloy and a Mg-Al alloy. In other embodiments, the magnesium-containing alloy may be selected from Si-Mg alloys, rare earth Si-Mg alloys, Mg-Fe alloys, and the like, which are conceivable to those skilled in the art, and are not listed here.
The applicant finds in the course of the invention that: vacuum treatment is generally adopted when high-quality clean steel such as pipeline steel and the like is smelted in industrial production, no matter in RH or VD process, explosion safety problem can be caused by directly adding Mg, the Mg has low density and can be on the surface of molten steel when being added, meanwhile, the boiling point of the Mg is low, the Mg is gasified before being added and is difficult to dissolve in the molten steel, in addition, the chemical activity of the Mg is very strong, the Mg can be combined with oxygen and sulfur nitrogen to lose alloying effect, the Mg is vaporized before contacting the molten steel at the steelmaking temperature and forms high-pressure Mg steam, the steam pressure formed by gasifying the Mg reaches 1.86MPa, and violent oxidation can be generated by oxygen to generate explosion, so that the Mg is dangerous when being directly added into the molten steel, and how to safely add the Mg into the molten steel becomes the technical problem which needs to be solved in the Mg adding process.
By adopting the design, the characteristics of low melting point, small density, high vapor pressure, active chemical property and the like of Mg elements are overcome by changing the adding form of Mg, the problem of safe Mg addition is solved by adopting a method of increasing the melting point and the density and reducing the vapor pressure and the chemical activity, and the safe Mg addition is realized by adopting an intermediate alloy form of Ni-Mg, Mg-Al and the like. In practice, the Ni — Mg alloy is generally selected to have a composition comprising, by weight: ni 70-90% and Mg 10-30%, wherein the selected Mg-Al alloy comprises the following components: al 40-50%, Mg 10-15%, and Fe in balance.
The method for adding magnesium-containing alloy into molten aluminum killed steel is divided into two modes, namely a feeding method and a wire feeding method.
As an alternative embodiment, the method for adding the magnesium-containing alloy into the molten aluminum-killed steel is a charging method, and the charging method specifically comprises the following steps: and putting the magnesium-containing alloy into the molten aluminum-killed steel in a protective gas atmosphere, wherein the pressure of the protective gas atmosphere is as follows: 40-100KPa, and the granularity of the magnesium-containing alloy is less than or equal to 30 mm. Specifically, the protective gas atmosphere may be argon, nitrogen, or CO2Etc.; it should be noted that no protective atmosphere is required under atmospheric pressure, and the atmosphere is protected when the closed vessel is melted, such as under vacuum.
The effect of protective gas atmosphere inhibits the evaporation of magnesium, Mg is particularly active in the process of directly adding into molten steel under vacuum, eruption occurs when the Mg is serious, protective gas with certain pressure is filled into a smelting space, the evaporation of Mg is inhibited, the higher the pressure is, the higher the Mg yield is, and the pressure for controlling the protective gas atmosphere is: the reason for 40-100KPa is that the cost is too high when the air pressure is too large, and the adverse effect of too small is insufficient pressure and insufficient inhibition of Mg volatilization.
The reason for controlling the granularity of the magnesium-containing alloy to be less than or equal to 30mm is that the granularity of the Mg alloy is too large, and when molten steel is added, the local Mg vapor pressure of the molten steel is large, so that the molten steel is easy to erupt, and the yield of the alloy is unfavorable. When the alloy cored wire is added, the Mg alloy particle size wrapped by the alloy wire is smaller, and the size is generally below 5 mm.
As an alternative embodiment, the method for adding the magnesium-containing alloy into the molten aluminum killed steel comprises a wire feeding method, and the wire feeding method specifically comprises the following steps: feeding the aluminum killed steel molten steel into a magnesium-containing alloy core-spun yarn, wherein the granularity of the magnesium-containing alloy is 1-3 mm.
The reason for controlling the granularity of the magnesium-containing alloy to be 1mm-3mm is to consider that the comprehensive alloy yield is higher, the adverse effect of overlarge granularity value is that the local steam pressure of the alloy is high, the Mg element is quickly evaporated, the adverse effect of undersize is that the specific gravity is too low and is taken away by high-temperature steam, and both the alloy yield and the magnesium-containing alloy can cause the alloy yield to be reduced.
The applicant finds in the course of the invention that: the sizes of inclusions existing in the existing Ca-treated aluminum killed steel are still found to be large, the inclusions are not completely removed after the Ca treatment, the Mg yield is low in the Mg treatment before the vacuum premise, the Mg content in the steel is extremely low or too high after the vacuum Mg treatment, so that the quality of the product is unstable, the effect of the inclusion modification process is influenced, and the problem of how to define the proper Mg content to ensure the inclusion modification effect is solved.
In this embodiment, the amount of the wire feeding of the magnesium-containing alloy cored wire is 0.0002% to 0.0018% of the molten aluminum killed steel by weight; the wire feeding depth of the magnesium-containing alloy cored wire is 0.6-0.8 time of the depth of the molten steel; the wire feeding speed of the magnesium-containing alloy cored wire is 3m/s-6 m/s.
According to Al present in the molten steel2O3Determination of the content of inclusions and Al2O3The minimum Mg content wire feeding amount required by the modification of the inclusion, the excessive adverse effect of the wire feeding amount is that the wire feeding cost is high, single-particle MgO and other inclusions can be generated when the Mg is high, in addition, the Mg content in the added molten steel is difficult to reach more than 0.0018 percent, and the excessive adverse effect is that a large amount of harmful Al in the steel cannot be influenced2O3Modifying the impurities.
The reason for controlling the wire feeding depth of the magnesium-containing alloy cored wire to be 0.6-0.8 time of the depth of the molten steel is to ensure that effective content of Mg alloy enters the molten steel under the condition of safety and no occurrence of violent boiling of the molten steel, the adverse effect of overlarge depth value is influenced by the activity of the Mg alloy, the violent boiling of the molten steel exists, the adverse effect of undersize is that the Mg alloy wire cannot reach the inside of the molten steel, magnesium vapor quickly floats to the upper layer of the molten steel, homogenization cannot be realized, and the yield is low.
The reason for controlling the wire feeding speed of the magnesium-containing alloy cored wire to be 3m/s-6m/s is to safely and efficiently control the safety of the wire feeding process and stabilize the yield of Mg, the adverse effect of overlarge speed value is that the molten steel is violently boiled due to a large amount of Mg steam in the molten steel, the safety is affected, meanwhile, the local Mg content is high, part of Mg directly generates MgO, the useful Mg content for modification is reduced, and the adverse effect of undersize is that the smelting period is prolonged, and the production efficiency is reduced.
In the embodiment, after the wire feeding is finished, the molten aluminum killed steel is subjected to soft argon blowing, wherein the time for soft argon blowing is 3-8 min.
The soft argon blowing has the effect of promoting the homogenization and modification effects of the alloy, and the reason for controlling the soft argon blowing time to be 3-8 min is to save the time as much as possible on the premise of ensuring the homogenization and modification effects of the alloy.
As an alternative embodiment, the timing of the magnesium treatment is: after molten steel of the aluminum killed steel is subjected to slag deoxidation, molten steel sulfur reduction and molten steel alloying fine adjustment operation.
Analysis of the effect of molten steel conditions on Mg treatment should ensure effective Mg-to-Al in the steel2O3Deformation treatment, wherein Mg is lost by oxygen in slag and molten steel, and in order to reduce the loss of Mg consumption caused by oxidation of slag and molten steel, the oxygen potential of the slag needs to be ensured to be lower before Mg is added, and Mg treatment is preferably carried out after slag modification (white slag making), deoxidation and fine adjustment of all alloying are finished; meanwhile, in actual operation, it should be noted that: the molten steel treated by Mg should not stay for a long time, so that the pollution and secondary oxidation of the furnace lining to the low-oxygen clean molten steel after Mg treatment are reduced. In addition, too high S content in the molten steel before Mg treatment can also affect the modification of Mg to oxidesThe sexual effect is that Mg in the molten steel with lower oxygen content can be combined with S in the steel to form MgS inclusion, thereby influencing the direct Al-to-Mg ratio2O3And (5) deformation processing. Also, higher molten steel temperatures are detrimental to Mg processing yields. In summary, the molten steel state before Mg treatment should be maintained at a proper temperature, low oxygen and sulfur contents, and all alloying adjustments are completed, and specifically, the oxygen content in the molten steel is preferably less than 0.003% and the sulfur content in the molten steel is preferably less than 0.003%, and the temperature is preferably controlled to be less than 80 ℃ of the superheat degree of the molten steel, and preferably, the temperature of the molten steel is a low temperature.
In conclusion, in combination with the production of the steel-making industry, certain top slag modification and molten steel deoxidation are required before feeding the Mg wire, the oxygen potential of the slag is reduced to produce the oxygen content in white slag and molten steel, and the top slag modification and the molten steel are also required to be placed after LF refining or vacuum refining is finished in the process sequence. Taking the pipeline steel as an example, the pipeline steel process comprises the following steps: smelting → LF → RH (VD) refining → continuous casting, which needs to be carried out under the atmospheric pressure after vacuum treatment, in order to ensure less splashing in the process of adding Mg wire, in the actual operation, the speed can be reduced when the Mg alloy wire is fed initially, and the speed is gradually increased after the liquid level of the added Mg alloy wire boils stably, so that a balance speed is found through practice. And after feeding the Mg wire, performing bottom blowing Ar3-8 minutes to promote the uniformity of alloy elements and the Mg treatment effect. In order to ensure the Mg treatment effect, the electric spark direct-reading spectrum analyzer is used for quickly analyzing the steel-making molten steel samples by utilizing Mg-containing standard samples.
The method for producing the low-inclusion aluminum killed steel of the present application will be described in detail below with reference to examples, comparative examples and experimental data.
Example 1
The process flow adopted in the production of the pipeline steel liquid magnesium treatment is as follows: blast furnace molten iron → molten iron desulphurization → converter top and bottom combined blowing → LF furnace → RH (Mg) treatment → continuous casting. The pipeline steel completes the tasks of deoxidation and desulfurization in the steel-making LF furnace, and carries out slag modification on the slag at the top of the steel ladle, so that the oxidability of the slag is greatly reduced, and the gas harmful element N, H, O in the steel is further reduced by vacuum RH treatment, thereby providing good thermodynamic conditions for the treatment of molten steel magnesium.
The process of carrying out the Mg wire feeding operation at the RH wire feeding station comprises the following steps:
(1) the Mg processing alloy wire can select Ni-Mg alloy wire or Al-Mg alloy wire aiming at the Ni-containing pipeline steel, the Ni-free pipeline steel only uses the Al-Mg alloy wire, the Al-Mg alloy wire is Mg 10-15%, Al 40-50% and the rest Fe, the outer diameter of the core-spun wire is 13mm, and the thickness of the steel strip is 0.4 mm.
(1) The wire feeding mode of the steel ladle is shown in the attached drawing 2-4 in detail, the weight of molten steel in the steel ladle is 278 tons, the wire feeding operation is carried out after the vacuum treatment is finished, a furnace cover of the steel ladle is opened, and a wire feeder feeds Mg-Al wires for 300-450 meters. Soft blowing is started before wire feeding to enable molten steel to flow circularly, argon blowing strength is increased to the central slag surface of a steel ladle when the wire feeding is carried out, the molten steel is blown open, the wire feeding depth is about 0.60-0.80H (the molten steel depth), the wire feeding speed is 3-6 m/s, argon is soft blown for 3-8 minutes after the wire feeding, the alloy homogenization and modification effects are promoted, and the alloy increment of the fed Mg wire is shown in the following table;
and continuously casting molten steel after the pipeline steel is subjected to Mg treatment, and heating and rolling to obtain a finished product with the thickness of 12.7 mm.
The impurities in the steel in the rolled state are analyzed, as shown in figure 6, the main impurities in the steel do not have impurities with the large size being more than or equal to 15 mu m, and the impurities are mainly granular MgO-Al2O3And granular MgO & Al with enriched sulfide on surface2O3。
Example 2
The technological process adopted during the magnesium treatment production of wheel steel liquid comprises the following steps: blast furnace molten iron → molten iron desulphurization → converter smelting → argon blowing → LF furnace (Mg treatment) → continuous casting steel. The wheel steel completes the tasks of deoxidation and desulfurization in the steel-making LF furnace, and carries out slag modification on the slag at the top of the steel ladle, so that the oxidability of the slag is greatly reduced, and good thermodynamic conditions are provided for the treatment of molten steel magnesium after the LF furnace.
The process of carrying out Mg wire feeding operation at the LF wire feeding station comprises the following steps:
(1) the Mg treatment uses Al-Mg alloy wires, the Al-Mg alloy wires comprise 10-15% of Mg, 40-50% of Al and the balance Fe, the outer diameter of the cored wire is 13mm, and the thickness of the steel strip is 0.4 mm.
(2) The wire feeding process of the steel ladle is shown in the attached drawing 1, the weight of molten steel in the steel ladle is 278 tons, the wire feeding operation is carried out after LF treatment is finished, a furnace cover of the steel ladle is opened, and Mg-Al wires are fed for 200-600 meters through a wire feeding machine. Soft blowing is started before wire feeding to enable molten steel to flow circularly, argon blowing strength is increased to the central slag surface of a steel ladle when the wire feeding is carried out, the molten steel is blown open, the wire feeding depth is about 0.60-0.80H (the molten steel depth), the wire feeding speed is 3-6 m/s, argon is soft blown for 3-8 minutes after the wire feeding, the alloy homogenization and modification effects are promoted, and the alloy increment of the fed Mg wire is shown in the following table;
and continuously casting molten steel after Mg treatment of the wheel steel, and heating and rolling to obtain a finished product with the thickness of 1.8-16.0 mmmm.
Performing surface scanning inclusion statistical analysis on inclusions in steel in a rolled state, wherein the main inclusions in the steel do not have inclusions with the large size of more than or equal to 15 mu m, and the inclusions are mainly granular MgO-Al2O3And granular MgO & Al with enriched sulfide on surface2O3。
Example 3
The process flow adopted when the aluminum deoxidation killed steel is produced by the electric furnace is as follows: electric furnace → VIM (vacuum induction furnace)/VD (vacuum degassing) (Mg treatment) → continuous casting/die casting. The aluminum deoxidized killed steel completes the tasks of deoxidation and desulfurization in an electric furnace, and the vacuum treatment is carried out in vacuum to further reduce the gas harmful element N, H, O in the steel. Vacuum Mg treatment is carried out subsequently. The specific process comprises the following steps:
(1) the Mg treatment uses Ni-Mg alloy, wherein Ni 90% and Mg 10% of the Ni-Mg alloy are added on the surface of molten steel by a top feeding method, and the granularity is 2-20 mm.
(2) Vacuum refining in a vacuum furnace, wherein the weight of molten steel is 500kg, the components of the molten steel meet the target requirements, the total oxygen content in the steel is less than or equal to 0.003 percent, and then carrying out Mg treatment process in a vacuum chamber. Filling protective gas Ar gas (40-100) KPa before Mg treatment, then adding Ni-Mg alloy, after adding the alloy, increasing power, performing electromagnetic stirring for 1-3 minutes to promote the homogenization of the alloy, and then casting into ingots. The content of the finished product in the steel is shown in the following table.
And hot rolling the steel ingot treated by the electric furnace Mg into a finished product with the thickness of 12-25.4 mmm.
The statistical analysis of surface scanning inclusions in the steel in a rolled state is carried out, the main inclusions in the steel have no inclusion with the size larger than or equal to 15 mu m, which shows that only 0.0002 percent of Mg in the steel has effectively modified the inclusions, and the inclusions are mainly granular MgO. Al2O3And granular MgO & Al with enriched sulfide on surface2O3。
Comparative example 1
The process flow adopted during the production of the pipeline molten steel is as follows: blast furnace molten iron → molten iron desulphurization → converter top and bottom combined blowing → LF furnace → RH (Mg) treatment → continuous casting.
Performing surface scanning inclusion statistical analysis on inclusions in steel in a rolled state, wherein the distribution of the inclusions is shown as Al in figure 52O3The cluster inclusions existing in the steel are distributed in the rolling direction after hot rolling deformation, and the size is large.
Comparative example 2
The process flow adopted in the production of pipeline steel liquid calcium treatment is as follows: blast furnace molten iron → molten iron desulphurization → converter top and bottom combined blowing → LF furnace → RH (Ca) treatment → continuous casting.
Detailed description of the drawings 7-8:
as shown in FIGS. 2 to 8, which are ternary phase diagrams of inclusions in the steel after the treatment at magnesium addition levels of 0.0002%, 0.0004%, 0.0018% and 0.0022%, MgO. Al in the steel increases as the Mg content in the steel increases from 0.0002%, 0.0004%, 0.0018% and 0.0022%, respectively2O3Mg content of spinel gradually increases, unmodified Al2O3Gradually decreaseLess. However, when the Mg content in the steel reaches 0.0022%, 10 to 15 μm in the steel tends to increase, so that the Mg content is preferably 0.0002 to 0.0018%.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
(1) according to the method provided by the embodiment of the invention, pure magnesium is passivated to prepare alloy forms such as Al-Mg (Al 40-50%, Mg 10-15%), Ni-Mg (Ni 70-90%, Mg 10-30%) and the like, so that the problems of easy explosion and the like caused by direct magnesium addition are solved, the magnesium treatment of molten steel can be realized under normal pressure, and safe magnesium addition can also be realized under negative pressure;
(2) the method provided by the embodiment of the invention provides a whole set of process technologies such as raw material preparation, adding station, method and adding amount for Mg treatment industrial application, breaks through the current experimental and basic theory research stage, and realizes industrial technology popularization and application;
(3) according to the method provided by the embodiment of the invention, the wire feeding machine is used for carrying out LF or RH vacuum treatment and then carrying out normal pressure treatment, before Mg treatment, slag deoxidation, molten steel deoxidation and sulfur reduction operations are required, the wire feeding amount is about 0.0002-0.0018%, the depth is about 0.60-0.80H (molten steel depth), the wire feeding speed is 3-6 m/s, argon is softly blown for 3-8 minutes after wire feeding, the Mg treatment can achieve a good modification effect, and inclusions with the size larger than or equal to 15 mu m are not found in steel;
(4) the method provided by the embodiment of the invention can realize molten steel magnesium treatment by adopting a feeding method under the vacuum negative pressure smelting atmosphere, the operations of molten steel deoxidation and sulfur reduction are required to be completed before Mg treatment, magnesium alloy is fed after protective atmosphere (40-100) KPa is filled, the size of inclusions in steel is refined, and the molten steel is modified into small-size granular MgO-Al2O3And MgO. Al2O3-S。
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.
Claims (10)
1. A method of making a low inclusion aluminum killed steel, the method comprising:
smelting and continuously casting molten aluminum killed steel to obtain aluminum killed steel;
wherein, in the process of smelting the molten aluminum killed steel, the molten aluminum killed steel is subjected to magnesium treatment to reduce inclusions in the molten aluminum killed steel, and the magnesium treatment comprises adding magnesium-containing alloy into the molten aluminum killed steel.
2. The method of producing a low-inclusion aluminum-killed steel as claimed in claim 1, wherein said magnesium-containing alloy includes at least one of a Ni-Mg alloy and a Mg-Al alloy.
3. The method of producing a low-inclusion aluminum killed steel as claimed in claim 2, wherein said Ni-Mg alloy has a composition comprising, by weight: ni 70-90% and Mg 10-30%; the Mg-Al alloy comprises the following components: al 40-50%, Mg 10-15%, and Fe in balance.
4. The method for producing aluminum-killed steel with low inclusions as claimed in claim 1, wherein the manner of adding magnesium-containing alloy to the molten aluminum-killed steel includes a charging method, and the charging method specifically includes: and putting the magnesium-containing alloy into the molten aluminum-killed steel in a protective gas atmosphere, wherein the pressure of the protective gas atmosphere is as follows: 40-100KPa, and the granularity of the magnesium-containing alloy is less than or equal to 30 mm.
5. The method for preparing the aluminum-killed steel with low inclusions according to claim 1, wherein the manner of adding the magnesium-containing alloy into the molten aluminum-killed steel comprises a wire feeding method, and the wire feeding method specifically comprises the following steps: feeding the aluminum killed steel molten steel into a magnesium-containing alloy core-spun yarn, wherein the granularity of the magnesium-containing alloy is 1-3 mm.
6. The method of manufacturing aluminum killed steel with low inclusion according to claim 5, wherein the amount of the cored-wire containing magnesium alloy is 0.0002% -0.0018% of the molten steel of the aluminum killed steel by weight.
7. The method of manufacturing a low inclusion aluminum killed steel as claimed in claim 5, wherein said magnesium alloy cored-wire is fed to a depth of 0.6 to 0.8 times as large as the depth of molten steel.
8. The method of manufacturing a low inclusion aluminum killed steel as claimed in claim 5, wherein said magnesium alloy cored wire is fed at a speed of 3m/s to 6 m/s.
9. The method for manufacturing aluminum killed steel with low inclusions according to claim 5, wherein after the wire feeding is completed, the molten aluminum killed steel is subjected to soft argon blowing for 3-8 min.
10. The method of producing a low-inclusion aluminum-killed steel as claimed in claim 1, wherein said magnesium treatment is carried out at the timing of: after molten steel of the aluminum killed steel is subjected to slag deoxidation, molten steel sulfur reduction and molten steel alloying fine adjustment operation.
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