CN116479214B - Synthetic slag and preparation method and application thereof - Google Patents
Synthetic slag and preparation method and application thereof Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 161
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 83
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 83
- 239000004571 lime Substances 0.000 claims abstract description 83
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 72
- 239000010959 steel Substances 0.000 claims abstract description 72
- 238000003723 Smelting Methods 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 68
- 238000005266 casting Methods 0.000 claims abstract description 55
- 229910000532 Deoxidized steel Inorganic materials 0.000 claims abstract description 36
- 229910000655 Killed steel Inorganic materials 0.000 claims abstract description 30
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000009749 continuous casting Methods 0.000 claims abstract description 19
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 18
- 230000023556 desulfurization Effects 0.000 claims abstract description 18
- 238000003892 spreading Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000012216 screening Methods 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 76
- 238000010079 rubber tapping Methods 0.000 claims description 48
- 238000007670 refining Methods 0.000 claims description 47
- 229910052717 sulfur Inorganic materials 0.000 claims description 40
- 229910052742 iron Inorganic materials 0.000 claims description 39
- 229910000720 Silicomanganese Inorganic materials 0.000 claims description 37
- 239000011593 sulfur Substances 0.000 claims description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 27
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 27
- 239000010436 fluorite Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 21
- 239000005997 Calcium carbide Substances 0.000 claims description 14
- 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 claims description 14
- 238000007664 blowing Methods 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 6
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims description 6
- 238000005275 alloying Methods 0.000 claims description 6
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002421 finishing Substances 0.000 claims description 2
- 229910000914 Mn alloy Inorganic materials 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 12
- 238000004064 recycling Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000011084 recovery Methods 0.000 description 5
- 238000009628 steelmaking Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 229910004261 CaF 2 Inorganic materials 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910006639 Si—Mn Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002436 steel type Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 229910001341 Crude steel Inorganic materials 0.000 description 1
- 229910000677 High-carbon steel Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
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
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/076—Use of slags or fluxes as treating agents
-
- 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
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/02—Dephosphorising or 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
- C21C7/0006—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
- C21C7/04—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to the technical field of silicon-manganese alloy steel casting, in particular to synthetic slag and a preparation method and application thereof, wherein the preparation method comprises the following steps: spreading a layer of lime at the bottom of the mixing container in advance, pouring the silicon-manganese killed steel casting residues after continuous casting and pouring into the mixing container, and cooling the casting residues to below 500 ℃ according to the mass ratio of the silicon-manganese killed steel casting residues to the lime of 6-9:1-4, spreading a layer of lime on the slag surface; repeating the operations of deslagging and lime spreading, dedusting, cooling to the slag temperature below 80 ℃, crushing and screening to obtain the slag, wherein the upper slag surface and the lower slag surface of the silicon-manganese killed steel casting slag are covered with lime by adopting the method, and the components of the silicon-manganese killed steel casting slag and the precise control of the mass ratio of the silicon-manganese killed steel casting slag to lime are combined, so that the obtained synthetic slag is suitable for smelting silicon-manganese deoxidized steel, and has good desulfurization efficiency.
Description
Technical Field
The invention relates to the technical field of silicon-manganese alloy steel casting, in particular to synthetic slag and a preparation method and application thereof.
Background
The Si-Mn deoxidized steel is used as a typical representative steel grade of high-clean steel and is commonly used for producing automobile tire meridian and the like. Since manganese has a strong affinity with sulfur and inclusions (MnS) seriously affect the properties of the silicomanganese deoxidized steel, it is necessary to propose more methods for reducing the sulfur content in the silicomanganese deoxidized steel while recycling the casting residues. There are three methods for reducing sulfur content in ladle slag: a dilution method, a slag sucking method or a slag raking method, and a reducing agent method. The most widely used reducing agent method is currently used to deoxidize slag.
The steel slag is a main byproduct in the steelmaking process, the yield is about 8% -15% of the yield of the crude steel, the recycling of the steel slag is an important development direction of steel slag recycling, and the steel slag recycling rates in European Union and Japan reach 13.4% and 19.1% respectively. The refining slag is slag formed after molten steel refining is finished, has uniform components and a lower melting point, still has certain desulfurization capability and capability of adsorbing impurities in molten steel, and is the most valuable product in the slag recycling technology.
At present, the recycling technology of refining slag mainly comprises two modes of hot online recovery and cold processing recovery. The steel slag thermal state recovery technology has the following advantages: 1. recovering heat; 2. directly recycling the residual steel; 3. the process flow is simple and the cost is low. The patent document CN200610012345.4 discloses a method for recycling the steel-making casting waste heat state steel slag on line, which has the technical scheme that: the method sequentially comprises the following steps: a. pouring the residual heat state steel slag in the steel ladle into an empty steel ladle after pouring; b. tapping: conveying the ladle filled with the steel slag in a residual heat state to a converter, and tapping into the converter; c. refining; d. pouring. Pouring the residual heat state steel slag into an empty ladle for the next recycling. The sulfur capacity and the strong reducibility of the thermal state steel slag can be fully utilized, the slag system composition can be quickly adjusted, a low-melting-point slag system is formed, the fluidity of slag is improved, inclusions in molten steel are effectively absorbed, and the cleanliness of the molten steel is improved; the slag forming time of the high-alkalinity furnace slag is shortened, the alkalinity of ladle slag is improved, the desulfurization is facilitated, and the refining efficiency is improved; the electricity consumption and the cold slag consumption are reduced, and the production cost is reduced. However, the problems of time matching and difficult steel grade in the hot recovery process are that the solidification speed of refining slag is high, and the window time with good slag fluidity is less than 20min.
Therefore, some manufacturers also adopt a cold recovery mode of refining slag, for example, chinese patent document CN102896310A discloses a method for separating and recovering casting slag, wherein the casting slag and the participated molten steel are added into a slag pot paved with acid metallurgical waste, slag steel separation is realized after crushing and magnetic separation, so that modified casting slag with the alkalinity less than 2.0 is obtained, the alkalinity of the casting slag is low, meanwhile, cold steel is mixed in the cooling process, so that the oxidizing property of the casting slag is enhanced, and therefore, the steel slag prepared by the method is not suitable for desulfurization treatment of silico-manganese steel, the desulfurization effect is poor, and the target steel grade cannot be obtained.
Disclosure of Invention
The invention aims to overcome the defects that casting residues are not suitable for desulfurization treatment of silicomanganese deoxidized steel, the desulfurization effect is poor and target steel types cannot be obtained in the prior art, thereby providing synthetic slag and a preparation method and application thereof.
The invention provides a preparation method of synthetic slag, which comprises the following steps: spreading a layer of lime at the bottom of the mixing container in advance, pouring the silicon-manganese killed steel casting residues after continuous casting and pouring into the mixing container, and cooling the casting residues to below 500 ℃ according to the mass ratio of the silicon-manganese killed steel casting residues to the lime of 6-9:1-4, spreading a layer of lime on the slag surface, repeating the operations of deslagging and lime spreading, dedusting, cooling to the slag temperature below 80 ℃, crushing and screening to obtain the slag; the silicon-manganese killed steel casting slag comprises the following chemical components in percentage by mass: caO:50-60% of SiO 2 ：20-30%、MgO：4-8%、CaF 2 ：2-6%、MnO+T.Fe：≤3%、Al 2 O 3 Less than or equal to 3-10%, S less than or equal to 0.15%, and the balance of other unavoidable impurity components.
Further, the alkalinity of the silicomanganese killed steel casting residues is 2.0-3.0; and/or pouring out the casting residue at one time to be less than or equal to 1.5t.
Further, the silicomanganese killed steel casting slag is prepared by the following steps: KR molten iron pretreatment-converter or electric furnace smelting-LF refining-continuous casting;
preferably, after KR molten iron pretreatment, the sulfur content of molten iron is less than or equal to 0.0035 percent;
preferably, the sulfur content of the waste steel used in converter or electric furnace smelting is less than or equal to 0.015 percent, the waste steel ratio is 10-30 percent, and the sulfur content of converter tapping is less than or equal to 0.013 percent.
Wherein conventional techniques in the art are used for slagging during converter tapping and LF refining, such as adding conventional amounts of lime and fluorite. For example, lime 5.0-7.0kg/t and fluorite 1.0-2.0kg/t are added.
Further, the particle size of the lime is 5-20mm, wherein the mass ratio of the particle size smaller than 5mm is smaller than 5%, the mass ratio of the particle size larger than 20mm is smaller than 2%, and the CaO in the lime is more than or equal to 90% and the S is less than or equal to 0.05% according to the mass percentage.
Further, after sieving, bagging the particles with the particle size less than or equal to 5mm according to 100-1000 kg; 5-50mm particles are filled into a sealed tank and transported to a steel-making workshop for storage.
The invention also provides the synthetic slag prepared by any one of the preparation methods.
The invention also provides application of the synthetic slag prepared by any one of the preparation methods in smelting of the silicomanganese deoxidized steel.
The invention also provides a smelting method of the silicomanganese deoxidized steel, which comprises the steps of KR molten iron pretreatment, converter or electric furnace smelting by using synthetic slag, LF refining and continuous casting.
Further, the smelting method also satisfies at least one of the following A-F:
A. in KR molten iron pretreatment, when the sulfur content of molten iron is more than or equal to 0.04%, carrying out molten iron desulfurization treatment to ensure that the sulfur content of molten iron is less than 0.04%;
B. in the smelting tapping process, when the oxygen content of molten steel is less than or equal to 0.035%, adding 10.5-12.5kg/t of synthetic slag; when the oxygen content is more than 0.035%, adding 6.5-10.5kg/t of synthetic slag and 1.5-2.5kg/t of lime;
C. after smelting, the temperature of molten steel is 1620-1670 ℃, the oxygen content is 0.025-0.055%, and the S content is less than or equal to 0.035%;
D. when tapping begins, firstly adding ferrosilicon alloy, ferromanganese alloy and carbon powder for deoxidization alloying, and when the tapping amount reaches 60-70%, adding synthetic slag or adding synthetic slag and lime, and finishing charging before tapping ends;
E. the ladle bottom blowing flow rate in the tapping process is 300-600NL/min, the ladle bottom blowing flow rate in the tapping ending process is 800-1200NL/min, and stirring is carried out for 3-5min.
F. Adding fluorite, calcium carbide or lime according to the S content of the smelting finished product in the refining treatment process,
if the S content of the smelting finished product is less than or equal to 0.0035 percent, adding 1.0-1.5kg/t fluorite, 0.5-0.7kg/t calcium carbide and 1.5-2.0kg/t lime into the steel, setting the bottom blowing to be 500-600NL/min, and stirring for more than or equal to 15min; if the smelting finished product is 0.0035 percent and the S content is less than or equal to 0.010 percent, adding 0.5-1.0kg/t fluorite, 0.3-0.5kg/t calcium carbide, 1.0-1.5kg/t lime, setting 400-500NL/min by bottom blowing, and stirring for more than or equal to 10min; if the smelting finished product is 0.010 percent and the S content is less than or equal to 0.015 percent, 0.2 to 0.4kg/t of calcium carbide, 0.5 to 1.0kg/t of lime and 400 to 500NL/min of bottom blowing are added, and the stirring time is 5 to 10min.
The invention also provides the silicomanganese deoxidized steel prepared by the preparation method; preferably, the chemical components of the silicomanganese deoxidized steel comprise the following components in percentage by mass: c:0.2-0.9%, si:0.3-1.0%, mn:0.4-1.5%, P is less than or equal to 0.018%, S is less than or equal to 0.015%, cr:0-0.5%, al less than or equal to 0.005%, ti less than or equal to 0.0020%, and Fe and other unavoidable impurity elements.
The technical scheme of the invention has the following advantages:
1. the preparation method of the synthetic slag provided by the invention comprises the following steps: spreading a layer of lime at the bottom of the mixing container in advance, pouring the silicon-manganese killed steel casting residues after continuous casting and pouring into the mixing container, and cooling the casting residues to below 500 ℃ according to the mass ratio of the silicon-manganese killed steel casting residues to the lime of 6-9:1-4, spreading a layer of lime on the slag surface; repeating the operations of deslagging and lime spreading, dedusting, cooling to the slag temperature below 80 ℃, crushing and screening to obtain the slag; the silicon-manganese killed steel casting slag comprises the following chemical components in percentage by mass: caO:50-60% of SiO 2 ：20-30%、MgO：4-8%、CaF 2 ：2-6%、MnO+T.Fe：≤3%、Al 2 O 3 The method is characterized in that the upper slag surface and the lower slag surface of the silicon-manganese killed steel casting slag are covered with lime by the method, the components of the silicon-manganese killed steel casting slag and the mass ratio of the silicon-manganese killed steel casting slag to lime are combinedThe obtained synthetic slag is suitable for smelting the silicomanganese deoxidized steel, has good desulfurization efficiency, can obtain the silicomanganese deoxidized steel with the sulfur content meeting the requirement, solves the problem of tailings treatment, reduces the consumption of slag-making materials such as lime, fluorite and the like, and simultaneously, the casting residues are fully reacted in the refining process to form a slag system with low melting point, and the recycling is very beneficial to accelerating the melting of the slag and improving the smelting efficiency.
In addition, the hot casting slag is poured into a mixing container (such as a slag basin), a layer of lime is spread on a vertical horse, the preheating of the casting slag is utilized to react and fuse with fine lime powder, the drifting of lime powder particles is reduced, and the waste heat is utilized to the greatest extent.
2. According to the smelting method of the Si-Mn deoxidized steel, a large amount of SiO can be generated in the tapping deoxidization process of the converter and the electric furnace due to the Si-Mn deoxidized steel 2 After the synthetic slag is added, lime is not added, the synthetic slag can be directly added to keep stable slag components and alkalinity, and the slag melting can be completed by utilizing the heat of molten steel in the tapping process and mixing and stirring, so that the desulfurization treatment can be performed on the molten steel in advance. The refining efficiency is greatly improved, and the consumption of lime and fluorite is greatly reduced.
3. The smelting method of the silicomanganese deoxidized steel provided by the invention not only solves the problems that the steel grade and time of the hot refining slag recycling technology are not matched, the dosage cannot be controlled, the production is smooth and disturbed, and the like. Various components required by the synthetic slag are prepared in advance, a slag making process is designed, smelting efficiency is improved, and slag making consumption is reduced. The use method of the synthetic slag can greatly reduce the consumption of refined lime and fluorite, improve the refining efficiency and reduce the process energy consumption.
4. According to the smelting method of the silicomanganese deoxidized steel, after molten steel enters a station in a refining mode, slag in the ladle is observed to be completely melted and is in a white slag state, the product technological requirements are met, lime and fluorite are not needed to be added for further slag adjustment, more lime and fluorite are needed to be added compared with a non-added synthetic slag heat, the smelting method is not easy to melt, the stirring time is long, a large amount of fluorite and lime are needed to be added in the refining process, and the refining efficiency is low.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge. In the present invention, the O content, the S content, etc. are mass contents unless specified otherwise.
Examples 1-6 respectively provide a preparation method of synthetic slag and application of the synthetic slag in silicomanganese deoxidized steel smelting or a smelting method of silicomanganese deoxidized steel, and the synthetic slag of each example is prepared according to the following steps:
pouring the recovered silicon-manganese killed steel casting residues into a mixing container after continuous casting, and uniformly spreading a layer of fine lime powder (the mass ratio of the silicon-manganese killed steel casting residues to the lime powder is 6-9:1-4) at the bottom of the mixing container in advance, wherein the particle size of the lime powder is 5-20mm, the proportion of the lime powder is less than 5mm and less than 5%, the proportion of the lime powder is more than 20mm and less than 2%, caO in the lime powder is more than or equal to 90%, and S is less than or equal to 0.05%. Cooling the casting residue to below 500 ℃ (recorded as the cooling temperature of the casting residue), and then according to the mass ratio of the silicon-manganese killed steel casting residue to the lime powder of 6-9:1-4, spreading a layer of lime on the slag surface, repeating the operations of deslagging and lime spreading until the mixing container is full, covering lime powder on the surface of the casting residue, dedusting, cooling to the slag temperature below 80 ℃ (recorded as slag cooling temperature), crushing and screening to obtain synthetic slag. Bagging the particles with the particle size less than or equal to 5mm according to 100 kg; 5-50mm particles are filled into a sealed tank and transported to a steel-making workshop for storage. The cooling temperatures and the mass ratios of the silicon-manganese killed steel casting residues and the lime powder used in examples 1 to 6 are shown in table 1.
The silicon-manganese killed steel casting residue acquisition paths in examples 1-3 are as follows:
the recovered silicon-manganese killed steel casting residue is the refining residue left after C82DA smelting, and the C82DA smelting process route is as follows: KR molten iron pretreatment-converter/electric furnace smelting-LF refining-continuous casting, wherein KR carries out deep desulfurization treatment on molten iron, clean scrap steel smelting is adopted in a converter, lime and fluorite slag formation are adopted in the converter tapping and refining processes, and protective casting is adopted in continuous casting.
Wherein after KR molten iron pretreatment, the sulfur content of the molten iron is 0.0010-0.0035 percent, and the molten iron desulfurization slag is completely removed and then added into a converter for smelting; the sulfur content of the clean scrap steel used for the converter is 0.005-0.015%, the scrap steel ratio is 10-20%, and the sulfur content of the tapping steel of the converter is 0.003-0.010% (wherein, the sulfur content and the scrap steel ratio in the above steps in examples 1-3 are shown in Table 2). Adding ferrosilicon alloy, ferromanganese alloy and carbon powder for deoxidization alloying during converter tapping, adding lime and fluorite for slagging, and then conveying to refining for smelting; LF refining is carried out, lime, fluorite and calcium carbide are added for fine adjustment of slag components, and the obtained components are CaO:50-60% of SiO 2 ：20-30%、MgO：4-8%、CaF 2 ：2-6%、MnO+T.Fe：≤3%、Al 2 O 3 Less than or equal to 3-10%, S less than or equal to 0.15%, and the balance of other unavoidable impurity components, wherein the alkalinity of slag is 2.0-3.0, and the weight is 1.8-2.2t; and after refining, conveying molten steel to continuous casting, protecting casting, conveying the ladle to a slag basin for slag pouring, wherein the slag pouring amount is 1.0-1.5t, and pouring molten steel into the slag basin. The chemical components of the slag obtained in examples 1 to 3 are shown in table 3 in mass percent, and the balance is other unavoidable impurity components. And the basicity of the slag, the weight of the slag, and the amount of deslagging are shown in table 3.
The silicon-manganese killed steel casting residue acquisition paths in examples 4 to 6 are as follows:
the recovered silicon-manganese killed steel casting residue is the refining residue left after the smelting of 65Mn, and the 65Mn smelting process route is as follows: KR molten iron pretreatment-converter/electric furnace-LF refining-continuous casting, KR deep desulfurization treatment is carried out on molten iron, clean scrap steel is used for smelting in an electric furnace, lime and fluorite are used for slag formation in the refining process, and protection pouring is adopted for continuous casting.
After KR molten iron pretreatment, the sulfur content of the molten iron is 0.0015-0.0035 percent, removing the molten iron desulfurization slag, and adding the cleaned molten iron desulfurization slag into a converter for smelting; the sulfur content of clean scrap steel used for the converter is 0.015%, the scrap steel ratio is 20-30%, and the sulfur content of steel tapping of the converter is 0.005-0.013% (wherein, the sulfur content and the scrap steel ratio of the steps in examples 4-6 are shown in Table 2). Adding ferrosilicon alloy, ferromanganese alloy and carbon powder for deoxidization alloying during tapping by an electric furnace, adding lime and fluorite for slagging, and then conveying to refining for smelting; LF refining is carried out, lime, fluorite and calcium carbide are added for fine adjustment of slag components, and the obtained components are CaO:50-60% of SiO 2 ：20-30%、MgO：4-8%、CaF 2 ：2-6%、MnO+T.Fe：≤3%、Al 2 O 3 Less than or equal to 3 to 10 percent, S less than or equal to 0.15 percent, and the balance of other unavoidable impurity components, wherein the alkalinity of slag is 2.0 to 3.0, and the slag amount is 1.6 to 2.0t; and after refining, conveying molten steel to continuous casting, protecting casting, conveying the ladle to a slag basin for slag pouring, wherein the slag pouring amount is 0.8-1.3t, and pouring molten steel into the slag basin. The chemical compositions of the slag obtained in examples 4 to 6 are shown in table 3 in mass percent, and the balance is other unavoidable impurity components. And the basicity of the slag, the weight of the slag, and the amount of deslagging are shown in table 3.
The application of the synthetic slag in the smelting of the silicomanganese deoxidized steel or the smelting method of the silicomanganese deoxidized steel is as follows, and the synthetic slag with the thickness of 5-50mm obtained by recycling and processing is used for producing bead C84DA, SAE series steel wire ropes, 45, 70, 80 and other silicomanganese killed high-carbon steel.
Wherein the chemical components of the silicomanganese deoxidized steel comprise the following components in percentage by mass: c:0.2-0.9%, si:0.3-1.0%, mn:0.4-1.5%, P is less than or equal to 0.018%, S is less than or equal to 0.015%, cr:0-0.5%, al less than or equal to 0.005%, ti less than or equal to 0.0020%, and Fe and other unavoidable impurity elements. The chemical compositions of the silicomanganese deoxidized steel obtained in examples 1 to 6 are shown in table 4 in mass percent, and the balance is Fe and other unavoidable impurity elements.
The production process flow comprises the following steps: KR molten iron treatment, converter/electric furnace smelting, LF refining and continuous casting.
(a) KR molten iron treatment
The sulfur content of the initial molten iron and the sulfur content after desulfurization are shown in Table 5, and when the S content of the molten iron is more than or equal to 0.04%, the desulfurization treatment is carried out on the molten iron so that the sulfur content of the molten iron is less than 0.04%. Wherein the S content before and after desulphurizing the molten iron in examples 1-6 is shown in the following table 5.
(b) Converter and electric furnace smelting
Examples 1, 3 and 5 were smelted using a converter. Adding scrap steel in a converter by 10-20%, adding desulfurized molten iron into the converter for smelting, desilicating, dephosphorizing and decarbonizing in the converting process of the converter, tapping, wherein the temperature of molten steel is 1620-1655 ℃ after smelting is finished, the oxygen content is 0.025-0.055%, and S is less than or equal to 0.035%.
Examples 2, 4 and 6 were smelted using an electric furnace. Adding 20-30% of scrap steel into an electric furnace, adding desulfurized molten iron into the electric furnace for smelting, desilicating, dephosphorizing and decarbonizing in the electric furnace smelting process, tapping, and after smelting, obtaining molten steel with the temperature of 1640-1670 ℃, the oxygen content of 0.025-0.055% and the S less than or equal to 0.035%.
Wherein the smelting end point conditions of the converter in examples 1-6 are shown in the following table 6.
(c) Tapping process for converter and electric furnace
Examples 1, 3 and 5 control the converter end point conditions, and tapping and refining control conditions were determined based on the converter end point O, S content and the smelting target steel grade S content. When tapping begins, ferrosilicon alloy, ferromanganese alloy and carbon powder are added for deoxidization alloying, when the tapping amount reaches 65%, synthetic slag or synthetic slag and lime are added according to the following table 7, and the addition is completed before tapping is finished, stirring is continued, and stirring is stopped after the synthetic slag or the synthetic slag and lime are completely melted (complete melting means that the refining slag is in a red hot state and no blocky slag is observed by naked eyes). The stirring time after tapping is finished is the time from the addition of synthetic slag or synthetic slag and lime to complete melting.
Examples 2, 4 and 6 control conditions of the electric furnace end point, and tapping and refining control conditions were determined based on the content of O, S of the electric furnace end point and the content of S of the target steel grade for smelting. When tapping begins, ferrosilicon alloy, ferromanganese alloy and carbon powder are added for deoxidization alloying (the addition amount is determined according to the steel grade), when the tapping amount reaches 70%, synthetic slag or synthetic slag and lime are added, and the addition is completed before tapping is finished, stirring is continued, and stirring is stopped after the synthetic slag or the synthetic slag and the lime are completely melted (complete melting means that refining slag is completely red and hot and no blocky slag is observed by naked eyes). The stirring time after tapping is finished is the time from the addition of synthetic slag or synthetic slag and lime to complete melting.
Wherein the control conditions of the tapping of the converter in examples 1-6 are shown in the following table 7.
(d) LF refining process
And (5) conveying molten steel to LF refining for treatment after tapping of the converter or tapping of the electric furnace. Adding fluorite, calcium carbide or lime according to the S content in the smelting steel, and stirring for a period of time until the sulfur content of the molten steel meets the steel type requirement. Wherein the LF refining process control conditions in examples 1-6 are shown in Table 8 below.
(e) Continuous casting
The billet is obtained through a continuous casting process, and the superheat degree is controlled to be 15-35 ℃ in the continuous casting process.
Comparative examples 1 to 6
This comparative example 1 provides a method of smelting silicomanganese deoxidized steel, which is substantially the same as example 1, except that the following conditions are different in the converter tapping and LF refining processes, as shown in table 9 below.
This comparative example 2 provides a method of smelting a silicomanganese deoxidized steel, which is substantially the same as example 2 except that the following conditions are different in the electric furnace tapping and LF refining processes, as shown in table 9 below.
This comparative example 3 provides a method of smelting silicomanganese deoxidized steel, which is substantially the same as example 3 except that the following conditions are different in the converter tapping and LF refining processes, as shown in table 9 below.
This comparative example 4 provides a method of smelting a silicomanganese deoxidized steel, which is substantially the same as example 4 except that the following conditions are different in the electric furnace tapping and LF refining processes, as shown in table 9 below.
This comparative example 5 provides a method of smelting a silicomanganese deoxidized steel, which is substantially the same as example 5 except that the following conditions are different in the converter tapping and LF refining processes, as shown in table 9 below.
This comparative example 6 provides a method of smelting a silicomanganese deoxidized steel, which is substantially the same as example 6 except that the following conditions are different in the electric furnace tapping and LF refining processes, as shown in table 9 below.
In comparative examples 1 to 6, when the oxygen content of molten steel is less than or equal to 0.035% in the tapping process of a converter or an electric furnace, 5.0 to 7.0kg/t of lime and 1.0 to 2.0kg/t of fluorite are required to be added; when the oxygen content is more than 0.035%, lime is added in an amount of 6.5-8.5kg/t, fluorite is added in an amount of 1.5-2.5kg/t. Stirring for 5-7min.
In the LF refining treatment, if the S content of a smelting finished product is less than or equal to 0.0035 percent of steel grade, 1.0-2.0kg/t of fluorite, 0.7-1.0kg/t of calcium carbide, 2.5-3.5kg/t of lime and 500-600NL/min of bottom blowing are required to be added, and the stirring time is more than or equal to 25min; if the smelting finished product is 0.0035 percent and the S content is less than or equal to 0.010 percent, 0.5-1.0kg/t of fluorite, 0.5-0.7kg/t of calcium carbide and 1.5-2.5kg/t of lime are required to be added, the bottom blowing is set at 400-500NL/min, and the stirring time is more than or equal to 15min; if the smelting finished product is 0.010 percent and the S content is less than or equal to 0.015 percent, 0.3 to 0.5kg/t of calcium carbide, 1.0 to 1.5kg/t of lime and 400 to 500NL/min of bottom blowing are required to be added, and the stirring time is more than or equal to 20min.
Wherein the LF refining process control conditions in comparative examples 1 to 6 are shown in Table 10 below.
The high alkalinity low oxidation synthetic slag prepared by mixing the recovered silicon-manganese killed steel casting slag with lime powder with proper mass ratio in the embodiments 1-6 has low melting point and fast slag formation compared with the lime adopted in the comparative examples 1-6, and can be mixed with molten steel in a converter or electric furnace tapping process to be quickly melted to form proper ladle refining slag for desulfurizing the molten steel. The slag forming time is short; the consumption of lime and fluorite is low; high refining efficiency and low power consumption. Lime has high melting point, a large amount of lime is needed to be added for slagging when smelting low-sulfur and ultra-low-sulfur steel, lime is not easy to melt, fluorite can be added in a large amount only, and the slag is melted by electrifying, so that the problems of high slag material consumption, high electricity consumption, long smelting time and the like are solved.
The synthetic slag provided by the invention has remarkable use effect in the steelmaking process, and is very beneficial to reducing consumption and pollutant emission.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (8)
1. The smelting method of the silicomanganese deoxidized steel is characterized by comprising the steps of KR molten iron pretreatment, converter or electric furnace smelting by using synthetic slag, LF refining and continuous casting; the preparation method of the synthetic slag comprises the following steps:
spreading a layer of lime at the bottom of the mixing container in advance, pouring the silicon-manganese killed steel casting residues after continuous casting and pouring into the mixing container, and cooling the casting residues to below 500 ℃ according to the mass ratio of the silicon-manganese killed steel casting residues to the lime of 6-9:1-4, spreading a layer of lime on the slag surface; repeating the operations of deslagging and lime spreading, dedusting, cooling to the slag temperature below 80 ℃, crushing and screening to obtain the slag; the silicon-manganese killed steel casting slag comprises the following chemical components in percentage by mass: caO:50-60%, siO2:20-30%, mgO:4-8%, caF2:2-6%, mnO+T.Fe: less than or equal to 3 percent, al2O3:3-10%, S is less than or equal to 0.15%, and the balance is other unavoidable impurity components;
when tapping begins, firstly adding ferrosilicon alloy, ferromanganese alloy and carbon powder for deoxidization alloying, and when the tapping amount reaches 60-70%, adding synthetic slag or adding synthetic slag and lime, and finishing charging before tapping ends; in the smelting tapping process, when the oxygen content of molten steel is less than or equal to 0.035%, adding 10.5-12.5kg/t of synthetic slag; when the oxygen content is more than 0.035%, adding 6.5-10.5kg/t of synthetic slag and 1.5-2.5kg/t of lime; after smelting, the temperature of molten steel is 1620-1670 ℃, the oxygen content is 0.025-0.055%, and the S content is less than or equal to 0.035%;
adding fluorite, calcium carbide or lime according to the S content of the smelting finished product in the refining treatment process, and adding 1.0-1.5kg/t of fluorite, 0.5-0.7kg/t of calcium carbide and 1.5-2.0kg/t of lime if the S content of the smelting finished product is less than or equal to 0.0035 percent of steel grade, wherein the bottom blowing is set at 500-600NL/min, and the stirring time is more than or equal to 15min; if the smelting finished product is 0.0035 percent and the S content is less than or equal to 0.010 percent, adding 0.5-1.0kg/t fluorite, 0.3-0.5kg/t calcium carbide and 1.0-1.5kg/t lime, and setting 400-500NL/min by bottom blowing, wherein the stirring time is more than or equal to 10min for 15min; if the smelting finished product is 0.010 percent and the S content is less than or equal to 0.015 percent, 0.2 to 0.4kg/t of calcium carbide, 0.5 to 1.0kg/t of lime and 400 to 500NL/min of bottom blowing are added, and the stirring time is 5 to 10min;
the chemical components of the silicomanganese deoxidized steel comprise the following components in percentage by mass: c:0.2-0.9%, si:0.3-1.0%, mn:0.4-1.5%, P is less than or equal to 0.018%, S is less than or equal to 0.015%, cr:0-0.5%, al less than or equal to 0.005%, ti less than or equal to 0.0020%, and Fe and other unavoidable impurity elements.
2. The method for producing a silicomanganese deoxidized steel according to claim 1, wherein, in the pretreatment of KR molten iron, when the sulfur content of the molten iron is not less than 0.04%, the desulfurization treatment of the molten iron is performed so that the sulfur content of the molten iron is less than 0.04%.
3. The method for smelting the silicon-manganese deoxidized steel according to claim 1, wherein the ladle bottom blowing flow rate in the tapping process is 300-600NL/min, the ladle bottom blowing flow rate at the tapping end is 800-1200NL/min, and the stirring is carried out for 3-5min.
4. A method of smelting a silicomanganese deoxidized steel according to any one of claims 1 to 3, wherein the basicity of the silicomanganese killed steel casting slag is 2.0 to 3.0; and/or pouring out the casting residue at one time to be less than or equal to 1.5t.
5. A method of smelting a silicomanganese deoxidized steel according to any one of claims 1 to 3, wherein the silicomanganese killed steel casting slag is produced by: KR molten iron pretreatment-converter or electric furnace smelting-LF refining-continuous casting.
6. The method for smelting silicomanganese deoxidized steel according to claim 5, wherein after the KR molten iron is pretreated, the sulfur content of the molten iron is less than or equal to 0.0035%; and/or the sulfur content of the waste steel used in converter or electric furnace smelting is less than or equal to 0.015 percent, the waste steel ratio is 10-30 percent, and the sulfur content of converter tapping is less than or equal to 0.013 percent.
7. A method for smelting a silicomanganese deoxidized steel according to any one of claims 1 to 3, wherein the grain size of the lime is 5 to 20mm, the mass ratio of the grain size < 5mm is < 5%, the mass ratio of the grain size > 20mm is < 2%, and the CaO in the lime is not less than 90% and S is not more than 0.05% in terms of mass%.
8. A silicomanganese deoxidized steel produced by the smelting process of any one of claims 1 to 7.
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