CN100540685C - direct steel alloying method - Google Patents
direct steel alloying method Download PDFInfo
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- CN100540685C CN100540685C CNB2004800076274A CN200480007627A CN100540685C CN 100540685 C CN100540685 C CN 100540685C CN B2004800076274 A CNB2004800076274 A CN B2004800076274A CN 200480007627 A CN200480007627 A CN 200480007627A CN 100540685 C CN100540685 C CN 100540685C
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- reductive agent
- alloy element
- manganese
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 141
- 239000010959 steel Substances 0.000 title claims abstract description 141
- 238000000034 method Methods 0.000 title claims abstract description 89
- 238000005275 alloying Methods 0.000 title claims abstract description 60
- 239000002994 raw material Substances 0.000 claims abstract description 120
- 230000002829 reductive effect Effects 0.000 claims abstract description 120
- 229910052751 metal Inorganic materials 0.000 claims abstract description 115
- 239000002184 metal Substances 0.000 claims abstract description 115
- 239000000956 alloy Substances 0.000 claims abstract description 93
- 150000001875 compounds Chemical class 0.000 claims abstract description 93
- 239000011572 manganese Substances 0.000 claims abstract description 93
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 91
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 84
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 59
- 238000002844 melting Methods 0.000 claims abstract description 35
- 230000008018 melting Effects 0.000 claims abstract description 35
- 230000009467 reduction Effects 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000002893 slag Substances 0.000 claims description 75
- 239000000463 material Substances 0.000 claims description 45
- 238000005266 casting Methods 0.000 claims description 41
- 230000008569 process Effects 0.000 claims description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 29
- 229910052782 aluminium Inorganic materials 0.000 claims description 29
- 239000004411 aluminium Substances 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 229910052804 chromium Inorganic materials 0.000 claims description 24
- 239000011651 chromium Substances 0.000 claims description 24
- 238000010079 rubber tapping Methods 0.000 claims description 24
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 23
- 239000003575 carbonaceous material Substances 0.000 claims description 21
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 20
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 20
- 239000004571 lime Substances 0.000 claims description 20
- 230000004927 fusion Effects 0.000 claims description 18
- 239000011575 calcium Substances 0.000 claims description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 15
- 229910052791 calcium Inorganic materials 0.000 claims description 15
- 229910052755 nonmetal Inorganic materials 0.000 claims description 15
- 239000000155 melt Substances 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- QDLZHJXUBZCCAD-UHFFFAOYSA-N [Cr].[Mn] Chemical compound [Cr].[Mn] QDLZHJXUBZCCAD-UHFFFAOYSA-N 0.000 claims description 5
- 229910000604 Ferrochrome Inorganic materials 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 238000011084 recovery Methods 0.000 abstract description 30
- 239000012535 impurity Substances 0.000 abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 description 49
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 20
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 18
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 12
- 238000011946 reduction process Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000000292 calcium oxide Substances 0.000 description 9
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000000571 coke Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 150000004645 aluminates Chemical class 0.000 description 6
- 239000012634 fragment Substances 0.000 description 5
- 230000001603 reducing effect Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 3
- 229910000805 Pig iron Inorganic materials 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910005347 FeSi Inorganic materials 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- MJPUVFCFWDNTML-UHFFFAOYSA-N carbonic acid;niobium Chemical compound [Nb].OC(O)=O MJPUVFCFWDNTML-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- ASTZLJPZXLHCSM-UHFFFAOYSA-N dioxido(oxo)silane;manganese(2+) Chemical compound [Mn+2].[O-][Si]([O-])=O ASTZLJPZXLHCSM-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000009847 ladle furnace Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation 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
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
Direct steel alloying method of the present invention relates to Iron And Steel Industry, and can be used for the production of steel by means of DIRECT ALLOYING technology.Described direct steel alloying method is included in the steel melting furnace makes steel, and with the steel alloying that manganese will so make, described manganese is to be obtained by described oxide compound reduction during the interpolation of raw material that comprises Mn oxide and reductive agent and between the reaction period of the two.The reduction of manganese be be added into molten metal surface on the raw material of nonmetallic compound of next self-contained alloy element in the reduction of other alloy element combine and carry out; When the floor height of the raw material of the nonmetallic compound that comprises alloy element that is added reach total floor height 0.1～0.15 the time, add reductive agent; Reduction temperature maintains the yield temperature of the raw material that is added; Make the puddle of reductive agent continue to contact with the puddle of the raw material of the nonmetallic compound that comprises alloy element that is added, the add-on of reductive agent is to make it possible to guarantee that the mixture of the raw material that added and reductive agent has the amount of required thermal property.Described method can guarantee metal interalloy element high-recovery, reduced the pollution of nonmetallic impurity to steel, and improved its quality.
Description
Technical field
The present invention relates generally to ferrous metallurgy, and be applicable to and adopt DIRECT ALLOYING technology to carry out the production of steel.
Technical background
Worldwide, improve the quality of steel, the trend of especially producing the steel of carbon, gas and impurity with low levels even super low loading becomes more and more important, in order to make steel have desired parameters before casting, this makes at existing melting method, mainly is that (out-of-furnace) in handling variation taken place outside the stove.In this, be strict with steel and have predetermined composition, every kind of element has narrow content range simultaneously.For this reason, can guarantee that the method for the controlled alloy recovery and the property-modifying additive rate of recovery and processing step just have significant importance by steel.
In view of the following fact, promptly in traditional product steel practice, no matter Steel Grade to be produced, all carbon products is hanged down in fusion in steel melting furnace, in the rectification systems of steel, make product have desired parameters then, therefore before alloying, have the necessity of low carbon products being carried out deoxidation treatment.In this case, metal contains saturated nonmetallic impurity, the oxidation products of deoxygenation inevitably, and for modification or remove oxidation products, must take to require the expenditure of energy and the additional measures of material.Outer next step that handle of stove, the alloying of steel is accompanied by the formation of the nonmetallic impurity of some amount equally.Pre-deoxidation for steel is handled, and uses the material that does not form nonmetallic impurity, for example coke or coal, will cause a large amount of thermosteresis, this must compensate by before discharging the carbon containing work in-process being heated once more, and this has caused too high cost, and has damaged the quality of steel.
With manganese the traditional method that steel carries out alloying is comprised: in steel melting furnace with the steel fusion, tap to ladle, pack into alloying material and be blown into rare gas element, wherein, after metal tapping, ferroalloy industry low-phosphorous contained manganese slag, reductive agent and lime so that slag basicity is 2.0～3.5 amount is loaded on the melt surface in the ladle, on weld pool surface, inject 3～30 seconds (SU1044641 of oxygen then, international classification number C21C 7/00,1983).
Yet, this traditional method also is not suitable for the production of high-quality steel, this is because by after the tapping in the steel melting furnace, oxide material, manganese, reductive agent and the lime that will contain alloy addition is loaded in the casting ladle on the carbon containing surface of semi-finished simultaneously, be blown into oxygen control feasible and the steel alloying technology that manganese carries out subsequently and become difficult, reclaim the high-recovery of manganese and the acquisition of high desulfurization degree thereby hindered by steel.
After the degree of depth pre-deoxidation of metal, by handle the sulphur content that can reduce in the steel with sweetening material, this for example needs, and by they being carried out vigorous stirring sweetening material is farthest contacted with metal.
In traditional method, the slag of high basicity that form, that show certain sulfide capacity after the DIRECT ALLOYING of the steel that carries out with manganese, owing to lack violent stirring, thereby the steel desulfidation of the degree of depth can not be provided.
Therefore this method and be not suitable for and in steel, obtain low sulphur content.
When steel and manganese are carried out DIRECT ALLOYING, the oxygen that is injected on the metallic surface has improved the oxygen level in the metal, this increased reductive agent consumption, reduced the manganese recovery ratio in the molten metal, worsened desulfurization condition, and increased the pollution of oxide compound and sulfide nonmetallic impurity to steel, promptly damaged the quality of steel.
Add the rate of recovery that raw material can reduce alloy element, manganese jointly in casting ladle when the carbon containing work in-process are tapped, and should the fact with the uncontrollable quality of damaging steel of alloying technology speed.
When according to the produced in conventional processes steel, compare with the method for carrying out steel alloying with iron alloy, the efficient of steel melting furnace will reduce, this is because when the carbon containing work in-process are tapped from casting ladle, all raw materials are encased in the casting ladle, this makes alloying process longer, because the raw material that needs extra time fusion to be packed into.
The low-phosphorous manganese that contains in the manganese slag in the iron alloy production is chemically stable compound form, MnSiO
3When so that basicity of slag is 2.0～3.5 amount uses and consume lime, and before beginning, the reduction reaction of manganese with low-phosphorous when containing the manganese slag and joining in the casting ladle, in slag, formed the have high-melting-point stable compound of (above 1400 ℃) with Calucium Silicate powder and free lime.When going back manganese silicate with silicon, though lime have a chemical bond that helps destroy manganous silicate, in slag, still formed infusible Calucium Silicate powder Ca
2SiO
4And Ca
3SiO
5, and cause slag to have high melting temperature, this factor increased slag viscosity, reduced the rate of recovery of manganese, increased the content of nonmetallic impurity and damaged the quality of steel.
And the employed Mn oxide material that contains as alloying material costs an arm and a leg in traditional method, and is energy-intensive, needs to consume a large amount of electric energy because it is produced.
The another kind of traditional method of producing steel comprises: in steel melting furnace, fusion, deoxidation, alloying, production comprised silicon and aluminium as the molten metal of reductive agent, in molten metal with CaO/Mn
xO
y=0.6～1.2 ratio adds and contains the oxide mixture of Mn oxide and calcium oxide, use formed slag treatment molten metal when being dissolved in silicon in the metal and aluminium reducing manganese in casting ladle, and described processing is to be CaO/SiO making molten metal remain on basicity of slag
2Carry out under=0.7～1.8 the condition, further in molten metal, add siliceous reductive agent and oxide mixture (RU2096491 C1, international classification number C21C 7/00,1997) then.
In the method, the pre-deoxidation of metal and alloying are in steel melting furnace, carry out in the presence of oxidation slag and highly oxidized metal.This not only caused can with the oxygenant of ferriferous oxide reaction and the consuming excessively of alloy addition in the slag, and increased the pollution of removable hardly nonmetallic impurity (silicate, aluminate and the sulfide that comprise manganese and iron) to metal.In the method, with the reduction manganese that derives from Mn oxide metal is handled in casting ladle then, with siliceous reductive agent, ferro-silicon joins in the casting ladle simultaneously.The manganese reduction method is carried out with disperse state, and its enforcement needs the extra time inevitably.In addition, owing to added the new silicate that forms in the manganese reduction reaction, so the amount of preformed silicate, aluminate and sulfide increases in the steel melting furnace.When lacking the means that inclusion is carried out spheroidizing, and when having the high silica slag be formed on the metallic surface, this method can not be removed non-metallic inclusion to form slag from metallic object, this has caused increasing the pollution to metal of oxide compound and sulfide inclusion thing, and has damaged the quality of metal.
This method has produced disadvantageous condition for the reduction of manganese, because the oxide mixture that in molten metal, adds (wherein the amount of rock ballast additive (CaO) be amount of the mixture 1/2～2/3) worsened melting condition, increased required time and the heat of its fusion, it is believed that this point is quite important when the reductive agent that adds with oxide mixture has more SA material (silicon) for comparing with aluminium.The possible local superheating of the use of siliceous reductive agent and described mixture and reductive agent has when serious.The use of siliceous reductive agent is relevant with the possible local superheating of described mixture and reductive agent, and is therefore, relevant with its floating matter on the molten slag surface and fully react with oxygen in the atmosphere.Although it is inappreciable that siliceous reductive agent loses to gas phase, but the Si oxide that forms in the manganese reduction reaction has worsened manganese reductive thermodynamic condition, this has caused containing the increase that calcium oxide (lime) consumes, and has increased the energy expenditure that is used for heated oxide thing mixture.The thermal property of oxide mixture even combine with the aluminium and the silicon that join in advance in the molten metal, can not provide spontaneous reduction process, and owing to SiO in the slag
2Increasing of part is for the additive decrementation of the siliceous reductive agent of the chemical heat that affords redress has damaged the manganese reducing property.
Summary of the invention
The objective of the invention is provides improving one's methods of steel DIRECT ALLOYING by preparation method's optimization.The present invention has guaranteed to be used for simultaneously raw material that fusion adds and has carried out the favourable physics of reductive, chemistry and temperature condition, this improved metal interalloy element recovery, reduced the pollution of non-metallic inclusion to steel, and improved the quality of steel.
The objective of the invention is to obtain a kind of DIRECT ALLOYING method of steel, this method may further comprise the steps: in steel melting furnace with the steel fusion; Carry out the alloying of steel with manganese, described manganese is to be obtained by described oxide compound reduction during the interpolation of raw material that comprises Mn oxide and reductive agent and between the reaction period of the two, wherein according to the present invention, by oxide compound reduction manganese be be added into molten metal surface on the raw material of nonmetallic compound of next self-contained alloy element in the reduction of other alloy element combine and carry out; And/or combine with reduction and to carry out from the manganese of the raw material that comprises other nonmetal manganic compound that is added; When the floor height of the raw material that is added be total floor height 0.1～0.15 the time, begin to add reductive agent; Reduction temperature maintains the raw material that added and the melt temperature of reductive agent; Make the puddle of reductive agent continue to contact with the puddle of the raw material of the nonmetallic compound that comprises alloy element that is added, the add-on of reductive agent is to make it possible to guarantee that the raw material that added and the mixture of reductive agent have required thermal property.
The raw material that comprises the nonmetallic compound of alloy element preferably comprises the oxide compound or the carbonate of alloy element, or comprises their combination.
Reductive agent is preferably and contains aluminium or siliceous or material containing carbon, or for comprising the material of alkaline-earth metal, perhaps is their combination.
Comprise the charging of raw material of the nonmetallic compound of alloy element, preferably carry out continuously or in batches, the amount of each batch is not less than 0.1 of total flow.
In a direct steel alloying method of in steel melting furnace, carrying out, exceed by formula Δ t=33[Mn when molten metal has reached to compare with tapping temperature] during the temperature of definite value, wherein: Δ t is for surpassing the value of tapping temperature, ℃; [Mn] is the amount of institute's reductive manganese, weight percentage; 33 is experience factor, the preferred carbonaceous material that further adds slag making materials and be used as reductive agent, and preferably add: make the ratio of raw material, slag making materials and the carbonaceous material of the nonmetallic compound that comprises alloy element be respectively 1: (0.18～0.20) with such amount: (0.10～0.12), and preferably from steel melting furnace, remove the oxidation slag.
When carrying out the alloying of steel in steel melting furnace, raw material, slag making materials and the carbonaceous material that preferably will comprise the nonmetallic compound of alloy element add in batches, and the weight that comprises all each batches that supply raw material is 0.01～0.02 of molten metal weight.
When in casting ladle, implementing direct steel alloying method, preferably in casting ladle, add carbonaceous material in advance; Reductive agent is preferably aluminium; In alloying process, the preferred extra lime that adds is as slag making materials, and various components preferably adopt following weight percent: the raw material that comprises the nonmetallic compound of alloy element: 56～65; Aluminium: 12～16; Carbonaceous material: 5～7; Lime: surplus.
When carrying out the alloying of steel with chromium in casting ladle, the nonmetallic compound of other element is preferably chromium cpd, and this compound can join in the casting ladle during the molten metal tapping; The content of manganese and chromium all improves 0.1% in the Finished Steel in order to make, in the material of the nonmetallic compound that comprises these elements chromated oxide preferably with manganese-chromium than being that 1.1～1.2 amount adds, and as the aluminium of reductive agent preferably with carbide of calcium with 1: the ratio of (2.9～3.2) adds.
When carrying out the alloying of steel with chromium in casting ladle, the raw material that comprises chromated oxide is preferably the converter slag of medium carbon ferrochrome in producing.
The method according to this invention depends on following implementation principle, helps the augmenting response equilibrium constant according to the reduction of this principle reaction zone temperature, has therefore increased the thoroughness of reaction; For this reason, the method according to this invention is guaranteed following condition:
1. forming the minimal viscosity of slag, the DIRECT ALLOYING method keeps minimum temperature and the oxide compound of the oxide products of reduction reaction-the be included in active element in the reductive agent is had the blast furnace slag adsorptive power in the alloy element reduction reaction zone.
In whole reduction reaction process the initial action composition in the lasting existence of conversion zone: the raw material of packetize compound and reductive agent.
3. will take out through the reaction zone of reductive alloy element, and make it enter metallic object, and make the oxide compound of formed reductive agent active element enter the slag phase from reaction product.
Because alloy element can be dissolved in molten pig, for example manganese can ad infinitum be dissolved in the molten pig, can be melted metal immediately through reductive manganese particulate absorbs, and convection flow, always be present in the molten metal body, remove through reductive enrichment of element formed layer in molten metal body, therefore with respect to alloy element, manganese makes the composition equalization.In the presence of reductive manganese particulate, other reducible alloy element also can be dissolved in the metallic object consumingly, because reduction reaction occurs under the liquid-phase condition, does not therefore hinder them to be dissolved in the molten metal.
Providing the amount of required thermal characteristics (thermicity) to add reductive agent for the nonmetallic compound that comprises Mn oxide, other alloy element and/or the incoming mixture that comprises other nonmetal manganic compound and reductive agent.
Spontaneous reaction for the reduction reaction of the element that comes autoxidisable substance and carbonate, the specific latent heat source that need comprise the certain material mixture of the nonmetallic compound of alloy element and reductive agent, this thermal source not only can fused raw material and Reducing and Alloying element, and separating metal and the slag that is forming be mutually effectively.In the direct steel alloying of the material that uses the nonmetallic compound (alloy element is the form of oxide compound and carbonate) that comprises alloy element and reductive agent, can produce the favourable heat condition of reduction reaction process, because with exothermic reducing reaction heat, the internal surface of molten metal, steel melting furnace etc. can provide other thermal source.In this case, with the quantitative heat that is provided to reaction zone, can provide to prevent that highly active element, reductive agent from burning taking place and it is removed condition to gas phase.Therefore, can select the thermal characteristics of every kind of specific mixture, so that under the situation of reductive agent loss minimum, provide spontaneous reduction by test.
After adding reductive agent, the reductive agent surface is at first covered by slag and metal.But because the fusing point of reductive agent is lower than the fusing point of metal and slag, the reductive agent fusion, and this process is accompanied by breaking of accompanying shell, thereby between the even component of formed puddle of reductive agent and the alloying material that has been melted, formed the contact that continues, kept this contact constantly by the thermopositive reaction heat of alloy element reduction reaction.This can provide add the synchronous process of the reduction reaction of the fusion of raw material and alloy element.
Embodiment
Finish the DIRECT ALLOYING method of steel in the following manner.
Fused iron is packed in the steel melting furnace, and for example oxygen coverter, shaft arc furnace etc. add slag making materials (lime, rhombspar, spar) then, are blown into oxygen in melts.After taking out the oxidation slag, the raw material that will comprise the nonmetallic compound of Mn oxide, other alloy element and/or comprise other nonmetal manganic compound is charged on the surface of molten metal.Comprise slag that the raw material of nonmetallic compound can produce for manganese ore, concentrate, slag, iron alloy etc.The nonmetallic compound of other alloy element can be for comprising such as the oxide compound of alloy elements such as niobium, titanium, molybdenum, chromium or such as the compound of the carbonate of alloy elements such as oxygen titanium carbonitride, carbonic acid niobium, alkaline-earth metal etc., or their combination.The raw material that comprises the nonmetallic compound of alloy element can be continuously or fed batch, and according to the predetermined composition of steel, the amount of each batch is not less than 0.1 times of total flow.The fusion that supplies raw material and Reducing and Alloying element are thus carried out synchronously, instruct batch feed of the raw material of the nonmetallic compound that comprises alloy element in view of the above.Reduce batch material quantity that feeds intake, make it be lower than 0.1 of total flow, will hinder melting process, this is because thereby raw material scorification has increased the fusion time, cause utilizing of reductive agent insufficient, and reduced the rate of recovery of the molten metal of the element that obtains by the raw material reduction that comprises the alloy element compound.
When the floor height of the raw material of the nonmetallic compound that comprises alloy element that is added reach height overall 0.1～0.15 the time, begin to add reductive agent, and in the process that further adds raw material, continue to add reductive agent.
Reductive agent is for containing aluminium or siliceous or material containing carbon, or is one group of alkaline-earth metal, or their combination.According to selected reductive agent, its fragment is formed can be in 1.0-3.0mm～20-50mm or variation in larger scope.Add reductive agent with the amount that required thermal property can be provided for the mixture of the raw material that added and reductive agent.
Just make temperature be lower than the temperature of fused raw material, instruct the nonmetallic compound that comprises Mn oxide, other alloy element in view of the above and/or comprise the adding of the raw material of other nonmetal manganic compound at the described raw material of fused.
When the even component that has formed melt raw material; and when adding reductive agent in due course; these measures can guarantee that the concentrated of reduction process carries out; and the fusion that supplied raw material and the reduction of alloy element are carried out synchronously; this improved metal interalloy element the rate of recovery, reduced the pollution of non-metallic inclusion to steel, and improved the quality of steel.The raw material and the reductive agent that contain the nonmetallic compound of alloy element by the while fusion can effectively utilize reductive agent.This has promoted concentrated (intensive) performance of the liquid-phase reduction reaction of alloy element.
Add reductive agent comprise the raw material of nonmetallic compound of alloy element in adding during, can begin reduction reaction earlier, make between the even component of fused raw material of the melt portions of reductive agent and the formed nonmetallic compound that comprises alloy element and continue contact, and the fusion and the reduction reaction that are supplied raw material are carried out synchronously, prevented the transformation of reduction process to disperse state thus, described disperse state is attended by low speed and the increase that consumes of reduction process, reductive agent completely, non-metallic inclusion to the pollution of metal and the reduction of steel quality.
The floor height of preferably working as the alloying material that is added reach total floor height 0.1～0.15 the time begin to add reductive agent, this is because the fusing point of reductive agent is lower than the fusing point of the raw material of the nonmetallic compound that comprises alloy element.When the floor height at raw material reach total floor height 0.1 before when just beginning to add reductive agent, raw material will have no time fusing forming homogeneous phase, so the fused reductive agent can't participate in reduction reaction, this can cause its insufficient utilization.When the raw material layer of the compound that comprises alloy element tall and big in total floor height 0.15 the time add reductive agent, be worthless equally, this is because the homogeneous concentrated formation of the alloying raw material that added will be disturbed the method for synchronization of alloying melting raw materials and reduction reaction, and this reduction, non-metallic inclusion that can cause the alloy element rate of recovery of molten metal is to the pollution of metal with to the infringement of steel quality.
The reduction of alloy element is at the nonmetallic compound that comprises Mn oxide, other alloy element, and/or comprises and carry out under the melt temperature of raw material of other nonmetal manganic compound.
This can instruct by the following fact: in the presence of the puddle of the even component of alloying raw material and reductive agent, the thoroughness of reduction reaction increases, and temperature is minimized, these facts help the alloy element of metal the rate of recovery, reduced the pollution of non-metallic inclusion to metal, and improved the quality of steel.The method according to this invention, temperature do not increase to the melt temperature that is higher than raw material, and this is that reduction reaction also finishes substantially because when working as the melting raw materials that added and finishing.
The method according to this invention, the puddle that needs reductive agent and fused comprise between the even component of raw material of nonmetallic compound of alloy element and continue to contact, to keep the high-speed and thoroughness of reduction process.
When direct steel alloying process is when carrying out, when the refining blasting period stops and reach molten metal temperature above tapping temperature, take out the oxidation slag in steel melting furnaces such as for example converter.Before tapping, must reduce the oxidation slag viscosity, and compensate the calorific loss that thermo-negative reaction caused of carbothermic reduction of alloy element of raw material of nonmetallic compound of self-contained alloy element, instruct the supplementary heating of molten metal in view of the above.For each specific Steel Grade, molten metal temperature answers the value of over proof tapping temperature to be determined by following formula: Δ t=33[Mn], wherein: Δ t is the value above tapping temperature, ℃; [Mn] is the amount of institute's reductive manganese, mass percent; 33 is experience factor.When molten metal is heated to temperature required value, take out the oxidation slag, with following processing can make metal in the steel melting furnace return sulphur and the rephosphorization process minimizes.Then, in steel melting furnace, add raw material, slag making materials such as the lime of the nonmetallic compound comprise alloy element and as the carbonaceous material of reductive agent, the weight of each batch is 0.01～0.02 of molten metal weight in batches.The raw material that comprises the nonmetallic compound of alloy element is lump ore stone, concentrate, agglomerate, is preferably the fragment component of 20～50mm, and the carbonaceous material as reductive agent that is added is coke, coal, silicon carbide, carbide of calcium, or their combination.The add-on of carbonaceous material is selected from following ratio: raw material, slag making materials and the carbonaceous material of the nonmetallic compound that comprises alloy material that is added are respectively 1: (0.18～0.20): (0.10～0.12).Direct steel alloying is carried out continuously, instruct this ratio in view of the above.The increase of slag making raw material and carbon raw material consumption with reduction join the nonmetallic compound that comprises alloy element in the steel melting furnace material quantity, reduce molten metal interalloy element the rate of recovery, increase slag heterogeneity, worsened the process of thermal exchange and exchange of substance, all these have all damaged the mass property of steel because of the content that has increased non-metallic inclusion.The raw material that is added is reduced to and is lower than 1: (0.18～0.20): during the ratio of (0.10～0.12), can reduce in add-on, the physics that worsens reduction process and the chemical state of oxide compound CaO in steel melting furnace, the reduction molten metal the rate of recovery, and damage the quality of steel through the reductive alloy element.
To be applied to the raw material and the lime melting of the nonmetallic compound that comprises alloy element (for example manganese) on the molten metal surface, and between oxygen, chemical reaction has taken place as the carbon of reductive agent and slag-metal two-phase system, for example:
(FeO)+C＝[Fe]+CO (1)，
(MnO)+C＝[Mn]+CO (2)，
[O]+C＝CO (3)。
Gaseous product in all three reactions is a carbon monoxide, and it can make the slag bubbling and strengthen its affinability and upper metallization layer, thereby helps base metal to the strong absorption through reduction elements.
The carbon that comprises in metal and the slag and the endothermic nature of the reaction between oxygen do not have inhibited reaction, and this is because before beginning DIRECT ALLOYING process, depend on through the reductive metal aequum of manganese for example, metal have been preheating to the temperature that is higher than tapping temperature.
Reduction process is evenly carried out, instruct the weight of the raw material of each batch adding in view of the above, be 0.01～0.02 of molten metal weight.When batch weight be reduced to be lower than molten metal weight 0.01 the time, can worsen reduction process thermal conditions and thereby worsened material exchange process, this is because reduce at the deoxidation process of molten metal with the amount of the atmospheric CO of bubbling on slag and molten metal surface layer that carbon carries out forming in the reductive process to alloy element, this has damaged the thoroughness of alloy element reduction reaction, and damaged refining process, and because the increase of non-metallic inclusion content, the quality of gained metal will worsen.
Every batch weight increased to be higher than 0.02 of molten metal weight also be improper, this is because this can disturb heat exchanging process, and the heavy addition of the slag making materials in the raw material that adds owing to being included in causes the degeneration of slagging process, this can cause slag to thicken, increased the heterogeneity of slag, reduced the rate of recovery of alloy element, and damaged refining process, therefore, the amount of non-metallic inclusion increases in the metal, and has damaged the quality of steel.
In the DIRECT ALLOYING process of being implemented, from steel melting furnace, take out the suboxide metal.Therefore, the process that makes metal have predetermined composition can be regulated in metal because of the oxygen dissolution of a small amount of and premeasuring.This has significantly reduced the repeated measures number of times of observing for to the close limit content of any alloy element or modifying element.
When in casting ladle, carrying out the DIRECT ALLOYING process, when molten metal begins to tap from steel melting furnace, at first carbonaceous material is joined in the casting ladle, following then column weight amount per-cent adds the raw material of the nonmetallic compound that comprises alloy element, such as reductive agent such as aluminium with such as slag making materialses such as lime: the raw material that comprises the nonmetallic compound of alloy element: 56～65; Aluminium: 12～16; Carbon material: 5～7; Lime: surplus.
With carbonaceous material, for example coke or coal join in the casting ladle with the amount of 5～7 weight % of the total flow that joins the raw material in the casting ladle, and the desoxydatoin to metal can be provided, and make the oxygen level in the Finished Steel reach desired numerical value.
In addition, desoxydatoin and alloying process can be shortened alloying time with metal being tapped combine to the casting ladle, thereby reduce the fusion cycle.The minimizing that joins carbonaceous material content in the raw material of casting ladle can't cause desired deoxidation level, yet its content increases to and surpasses 7% cooling that can cause metal in the casting ladle, this be because the shortage of heat that thermopositive reaction produced with the calorific loss that thermo-negative reaction was caused between the oxygen in compensation carbon and the metal.
Add the raw material of the nonmetallic compound that comprises alloy element with the amount of 56～65 weight %, can guarantee the predetermined concentration of alloy element in steel.The consumption that can increase reductive agent (aluminium) with the raw material that adds the nonmetallic compound that comprises alloy element less than the amount of 56 weight %, and the consumption of the reductive agent that is used for extra metal deoxygenation that is accompanied by the generation of the nonmetal aluminate inclusion that is difficult to remove, the quality that this has worsened the casting cycle of steel and has damaged steel.Raw material consumption increases to above 65 weight % will reduce the rate of recovery that reclaims alloy element thus.
Consume the high-recovery that aluminium can provide alloy material with the amount of 12～16 weight %, and with can not form AlO and the Al that pollutes workshop condition substantially
2O
3The metal temperature of reactant gases product is compared, and the temperature in the reaction zone reduces.The Al that in the aluminum oxide reaction, produces
2O
3Combine the compound that is easy to remove with formation with CaO.
Finish in the following manner with the direct steel alloying method that chromium carries out.During molten metal is tapped from steel melting furnace, the raw material of the nonmetallic compound that comprises other element of chromated oxide form is joined in the casting ladle with Mn oxide and other nonmetal manganic compound.
Because chromated oxide has high-melting-point, the melt temperature that the existence of Mn oxide and other nonmetal manganic compound adds raw material because of having reduced in the raw material that is added has been improved thermal equilibrium and the physics and the chemical condition of the reduction reaction of alloy element.Must accelerate to comprise the fusing of the infusibility component of chromated oxide, instruct in view of the above during the metal tapping, component is united adding in casting ladle, and this has improved the homogenizing of slag phase and the reduction process of alloy element.
Manganese-chromium in the raw material of the nonmetallic compound that comprises these elements that is added than be 1.1～1.2 be used for make the content of gained steel manganese and chromium all improve 0.1% oxide compound that consumes, the optimum recovery rate (about 90%) of metal interalloy elemental chromium and manganese can be provided, thus improved steel chemical homogeneity, reduced metal oxidation level, reduced the amount of non-metallic inclusion and improved the quality of steel.In the raw material that is added the ratio of manganese-chromium be brought down below 1.1 can reason the viscosity that causes of fused solution phase oxide raw materials increase and the high heterogeneity of the deterioration of the reduction process dynamic conditions that causes and the slag that forms and make chromium and the deterioration of manganese reductive process parameter.This has damaged by the performance of oxide compound recovery alloy element, has reduced the slag adsorptive power to non-metallic inclusion, and has increased the pollution of non-metallic inclusion to metal.In the raw material that is added, make manganese-chromium and will cause the raw material of chromium-containing oxide to the dilution of slag, the absolute magnitude that reduction comprises the raw material of nonmetal manganic compound than increasing to above 1.2, thereby reduced the rate of recovery of manganese and chromium in the metal, this can cause the reduction of the chemical uniformity of metallic object interalloy element manganese and chromium, and has damaged the quality of steel.
Will be as the aluminium of reductive agent with carbide of calcium with 1: the ratio of (2.9～3.2) joins in the casting ladle.Must make the alloy element that has the different melting points raw material from each, the heat of the reduction reaction of chromium and manganese and dynamic conditions optimization instruct the selected ratio of raw material in view of the above.Since exist simultaneously between the oxygen of the carbon of carbide of calcium and fused raw material thermo-negative reaction and at aluminium and from the oxygen of raw material and be dissolved in thermopositive reaction between the oxygen in the metal, thereby correct thermal equilibrium is provided, thereby has improved the rate of recovery from the molten metal of the alloy element of the raw material that is added.In addition, be included in the calcium in the carbide of calcium and be dissolved in oxygen in the metal and sulphur between thermopositive reaction has taken place, thereby generate CaO and CaS respectively.This helps in the reduction process thermally equilibrated stable equally.The carbon of carbide of calcium and the reaction between the oxygen are attended by the formation of carbon monoxide bubble, and this bubble makes the molten slag bubbling, and have improved the recovery ability of slag to non-metallic inclusion, thereby have reduced their content in metal, and have improved the quality of steel.
Be included in still not effective reductor of calcium and sweetening agent in the carbide of calcium, and can promote the spheroidizing of aluminate, as the result that the reduction process of carrying out the metal desoxydatoin with aluminium and alloy element is carried out from its oxide compound combines, this aluminate is formed on the matallic surface layer.Can reclaim the aluminate of balling energetically with surperficial slag, this helps the quality that reduces non-metallic inclusion and improve steel.Join the sulfide that forms in part calcium in the casting ladle and the metal, normally MnS and FeS react, thereby changed their form, and simple sulfide (CaS) and the complicated calcium-passivation manganese and the sulfide of silicon have been formed, thereby reduced the amount and the sulphur content of nonmetal sulfide inclusion thing in the metal, and improved the quality of steel.Carbide of calcium is partly increased to above 3.2 and can damage the characteristic of reduction reaction process and the sulphur removal purified characteristic of metal because of the deterioration of hot state, increased the heterogeneity of slag, reduced adsorptive power to non-metallic inclusion, increased the metal of alloy element, the chemical heterogeneity of chromium and manganese, and damaged the quality of steel.Carbide of calcium partly is reduced to is lower than 2.9 temperature in reduction reaction zone that will raise, and may be accompanied by molten aluminum and swim on the molten slag surface, because AlO and Al
2The incomplete oxidation of the aluminium of O makes the oxygen reaction in aluminium and the atmosphere, has generated the gas cyaniding thing after its oxidizing reaction in gas phase.This has changed thermal equilibrium, worsened from the reduction reaction process characteristic of the alloy element of its oxide compound with calcium metal is carried out sulphur removal purified process characteristic, and has damaged workshop condition.Because the reduction of heteropical increase of slag and carbon monoxide bubble rabbling roaster slag intensity, change reductive agent components in proportions according to the present invention will worsen the dynamic regime of reduction reaction and refining of metal process, this can damage the recovery ability of slag to non-metallic inclusion, and has increased the pollution of non-metallic inclusion to metal.All of these factors taken together with respect to the content of alloy element all can damage steel chemical uniformity, worsen desulfidation, increase the content of non-metallic inclusion in the metal, and the quality of infringement steel.
Do not repel other the embodiment that comprises within the scope of the claims according to the above-mentioned embodiment of the inventive method, and can have any container of molten metal, for example implement in open hearth, casting ladle, the ladle furnace etc.
Embodiment 1
Carry out the method for the DIRECT ALLOYING of steel implements in capacity is the converter of 250t with manganese and chromium.Molten pig is charged in the converter with slag making materials lime, and this molten pig comprises, by weight percentage: C-4.42; Si-0.82; S-0.020; P-0.095; Iron-surplus.This lime comprises, by weight percentage: CaO-92.0; MgO-6.5; Other secondary impurity (OSI)-surplus.
The material that comprises other nonmetallic compound of Mn oxide and manganese is that the total content in clean element manganese is the material of 44.6 weight %.The material that comprises the nonmetallic compound of other alloy element is to comprise 70.81 weight %Cr
2O
3Chromated oxide.Reductive agent is alumina-bearing material and carbonaceous material.Alumina-bearing material is the slag of the undergage during aluminium is produced, and comprises, by weight percentage: Al
Metal-44.8; Volatile matter-surplus; Carbonaceous material is a coke, comprises, by weight percentage: C-85.9; S-0.47; Volatile matter-surplus.After in converter that liquid pig iron and slag making materials are packed into, in metal with 940N m
3/ minute flow velocity be blown into oxygen, the time is 8 minutes, and takes out the oxidation slag.Then, supply rate with 14.0kg/t (3500kg) adds the raw material that comprises Mn oxide and other nonmetal manganic compound, and add the raw material that comprises chromated oxide with the supply rate of 12kg/t (3000kg), both are the fragment of 10～20mm, and are charged to continuously on the surface of molten metal in the converter.When the floor height that is supplied raw material for its total height 0.1～0.15 the time, the reductive agent that adds 1785kg, promptly have the slag of undergage in the aluminium production of fragment of 20～30mm and the coke of the fragment that 465kg has 10～20mm, so that obtain mixing the required thermal characteristics of raw material of adding.Under the melt temperature of the raw material that mix to add, under the condition that continues to contact between the puddle that in whole reduction reaction process, makes reductive agent and the puddle of the raw material that is added, carry out the reduction reaction of alloy element.In order to produce steel with required composition, required alloying additive (copper and mickel) is joined in the converter, simultaneously reductor, ferro-silicon are joined in the casting ladle.
Finished Steel is cast the steel ingot of 12.5t, described steel ingot roll is become the thick sheet material of 10～20mm, and carry out metallurgical analysis.
Finished Steel has following composition, by weight percentage: C-0.11; Si-0.24; Mn-0.57; S-0.010; P-0.007; Al-0.025; Cr-0.60; Ni-0.70; Cu-0.46; The Fe-surplus.
The manganese recovery ratio of molten metal is 92.7%, and chromium recovery ratio is 89.8%.Non-metallic inclusion (representing with percentage ratio) is as follows to the pollution of steel: oxide compound 1.4; Sulfide 1.2; Silicate 1.3.
Embodiment 2 (for compare and implement near prior art (RU 2096491))
In the 250t converter with converter in desoxydatoin and the alloying of metal come together to carry out fusion.Comprise aluminium and silicon at 1690 ℃ of metals that do not contain slag of from converter, tapping.During tapping, with CaO: Mn
xO
yManganese ore (the Mn-48.0% of=1: 1 ratio; SiO
2-3.5%; Fe-3.4%; CaO-1.5%; Al
2O
3-2.5%; P-0.05%) and lime (CaO-90%); The mixture of the ferro-silicon of the carbon ferrochrome of Φ X-650 (FeCr650) level and Φ C-65 (FeSi 65) level joins in the casting ladle simultaneously.As method of the present invention,, nickel and copper are joined in the converter in order to produce steel with required composition.CaO/SiO when maintenance 10 minutes and gained slag
2Basicity=1.3 o'clock, Finished Steel has following composition, by weight percentage: C-0.15; Mn-0.51; Si-0.27; Al-0.003; Cr-0.54; Ni-0.72; Cu-0.55; S-0.017; P-0.015; The Fe-surplus.
Molten metal has reclaimed 71.2% manganese, 67.8% chromium, and non-metallic inclusion (representing with percentage ratio) is as follows to the pollution of steel: oxide compound 3.5; Sulfide 2.8; Silicate 2.0.
Use method of the present invention that the high-recovery of alloy element can be provided, and reduced the pollution of non-metallic inclusion steel.
Embodiment 3
1630 ℃; Carbon content is 0.03～0.05%, and manganese is 0.055%.The pig iron of 146t is poured in the converter.The temperature of the pig iron that is added is 1410 ℃, and comprises, by weight percentage: C-4.2; Si-0.85; Mn-0.57; S-0.016; P-0.021.Use oxygen with 120Nm melts
3/ minute flow velocity purged 22 minutes, reach with comparing up to the temperature of melts according to the tapping temperature of specification exceed by formula Δ t=33[Mn] temperature of definite value: Δ t=33[Mn], wherein: Δ t is for surpassing the value of tapping temperature, ℃; [Mn] serve as reasons amount of the raw material reductive manganese that comprises nonmetal manganic compound, weight percentage; 33 is experience factor.Specification based on melts is determined formula Δ t=33[Mn] in [Mn] value.In an embodiment, be 0.03～0.05% o'clock in carbon content, the manganese content before coming out of the stove should be 0.55%.Under such carbon content, when purging end, manganese content is generally 0.05～0.07% (being considered as 0.05%).So, determine that [Mn] value is 0.55-0.05=0.50%.By formula Δ t=33[Mn] determine that Δ t value is 16.5%.Because this reason, purging up to melt temperature is 1647 ℃.From converter, take out the oxidation slag then, to contain Mn oxide, comprise the raw material (lime) of other non-metallic inclusion and as the mixture of the coke of carbon containing reducer to be respectively 1: (0.18～0.20): the amount of the ratio of (0.10～0.12) adds, and the weight that comprises all each batches that supply raw material is 0.01～0.02 of molten metal weight.Temperature of melt metal is 1630 ℃ when the DIRECT ALLOYING process stops before tapping.Before tapping, metal comprises, by weight percentage: C-0.05; Mn-0.54; P-0.006; S-0.005.
Table 1 has shown the process feature and the result of this method.
The molten metal of tapping in the casting ladle has demonstrated suboxide coefficient and low sulfur content and low phosphorus content, and this has reduced the pollution of non-metallic inclusion to steel, and helps to improve the quality of Finished Steel.The manganese recovery ratio of molten metal is 81.7%.
Embodiment 4
The steel fusing that will have following composition, by weight percentage: C:0.09～0.12; Mn:0.40～0.65; Si:0.17～0.34; S:0.20; P:0.20.The molten metal that will produce in steel melting furnace is in the casting ladle of 5t with the non-oxidised form capacity of tapping.In the tapping process of molten metal, with carbonaceous material; Coke; Comprising the material and the material that comprises other nonmetal manganic compound of Mn oxide, is 44 weight % in the manganese total content in the clean element material; Aluminium and lime as reductive agent join in the casting ladle.With ratio according to the present invention raw material is encased in the casting ladle.Metal is cast the steel ingot of 1t.Before raw material is joined casting ladle and extract metal sample afterwards and carry out chemical analysis.Also from the rolling product of making by steel ingot, extract sample to determine the percentage ratio of non-metallic inclusion.
Steel by DIRECT ALLOYING method preparation of the present invention has shown metal interalloy element, the high-recovery of manganese (95.4%), and the low pollution of non-metallic inclusion.
Embodiment 5
Adopt the DIRECT ALLOYING method of steel in the electric steel stove of 100t, to carry out fusion with chromium according to the present invention.
In 1650 ℃ of casting ladles that molten metal tapped from steel melting furnace, and during tapping, the alloy element that comprises with the converter slag form in the amount adding medium carbon ferrochrome alloy production of 1200kg, the raw material of the nonmetallic compound of chromium, the chromium content of this raw material is counted 48.99 weight % with clean element, add the raw material that comprises Mn oxide and other nonmetal manganic compound with the amount with 1400kg, total manganese content of this raw material is counted 44 weight % with clean element.Also the carbide of calcium of the secondary aluminum of 370kg AB-86 level and the 1100kg ratio with 1: 3 is joined in the casting ladle.
Finished Steel is cast as the steel ingot of 12.5t, this steel ingot rolling is become the thick sheet material of 10～20mm and carries out metallurgical analysis.
Finished Steel has following composition, by weight percentage: C-0.11; Si-0.17; Mn-0.54; S-0.006; P-0.007; Al-0.023; Cr-0.61; Ni-0.70; Cu-0.53; The Fe-surplus.
The test result that joins the composition of raw material in the casting ladle and product steel is as shown in table 2.
Table 2
| The melts sequence number | 1 | 2 | 3 |
| Raw material is formed, weight %: the raw material that comprises the nonmetallic compound of alloy element | 56.0 | 60.0 | 65.0 |
| Coke | 5.0 | 6.0 | 7.0 |
| Aluminium | 12.0 | 14.0 | 12.0 |
| Lime | 27.0 | 20.0 | 12.0 |
| Manganese recovery ratio, % | 96.8 | 97.0 | 98.0 |
| Desulfurization degree, % | 64.2 | 58.4 | 61.0 |
| The maximum percentage ratio of non-metallic inclusion: the oxide compound of strip inclusion form | 1.9 | 1.8 | 1.8 |
| The point-like oxide compound | 1.4 | 1.6 | 1.5 |
| Sulfide | 2.3 | 2.5 | 2.4 |
In this embodiment, the rate of recovery of molten metal is: 91.2% chromium and 93.2% manganese.
Use direct steel alloying method can provide for main alloy element and have the low pollution of highly chemical inhomogeneity steel, height desulfurization degree and non-metallic inclusion steel with chromated oxide consumption of the present invention.
Claims (9)
1. the DIRECT ALLOYING method of a steel, this method comprises: in steel melting furnace with the steel fusion; Carry out the alloying of steel with manganese, described manganese is to be obtained by described oxide compound reduction during the interpolation of raw material that comprises Mn oxide and reductive agent and between the reaction period of the two, described method is characterised in that, the reduction of manganese be be added into molten metal surface on the raw material of nonmetallic compound of next self-contained alloy element in the reduction of other alloy element combine and carry out; And/or combine with reduction and to carry out from the manganese of the raw material that comprises other nonmetal manganic compound that is added; When the floor height of the raw material that is added be total floor height 0.1～0.15 the time, begin to add described reductive agent; Reduction temperature maintains the raw material that added and the melt temperature of reductive agent; Make the puddle of described reductive agent continue to contact with the puddle of the raw material of the nonmetallic compound that comprises alloy element that is added, the add-on of described reductive agent is to make it possible to guarantee that the mixture of the raw material that added and reductive agent has the amount of required thermal property.
2. the method for claim 1, the wherein said raw material that comprises the nonmetallic compound of alloy element contains the oxide compound or the carbonate of described alloy element, or their combination.
3. the method for claim 1, wherein said reductive agent be for containing aluminium or siliceous or material containing carbon, or for containing the material of alkaline-earth metal, perhaps be their combination.
4. the method for claim 1, the adding of the raw material of the wherein said nonmetallic compound that comprises alloy element is carried out continuously or is carried out in batches, and the amount of each batch is more than or equal to 0.1 of total flow.
5. as each described method of claim 1～4, in the direct steel alloying process of wherein in steel melting furnace, implementing, exceed by formula Δ t=33[Mn when molten metal has reached to compare with tapping temperature] during the temperature of definite value, further add in the steel melting furnace with slag making materials with as the carbonaceous material of reductive agent, add-on is that the ratio of the raw material, slag making materials and the carbonaceous material that make the nonmetallic compound that comprises alloy element is respectively 1: (0.18～0.20): (0.10～0.12); And the oxidation slag taken out from steel melting furnace, wherein: Δ t is for surpassing the value of tapping temperature, and its unit is ℃, and [Mn] is the amount of institute's reductive manganese, and by weight percentage, 33 is experience factor.
6. method as claimed in claim 5, wherein said raw material, slag making materials and the carbonaceous material that comprises the nonmetallic compound of alloy element adds in batches, comprise the weight of each batch of the raw material that adds to some extent be 0.01～0.02 of described molten metal weight.
7. as each described method of claim 1～3, in the direct steel alloying process of wherein in casting ladle, carrying out, in casting ladle, add carbonaceous material in addition; The reductive agent that is added is an aluminium; In alloying process, add lime in addition as slag former; Various components adopt following ratio, by weight percentage: the described raw material that comprises the nonmetallic compound of alloy element: 56～65; Aluminium: 12～16; Carbonaceous material: 5～7; Lime: surplus.
8. as claim 1 or 3 described methods, wherein when carrying out the alloying of steel with chromium in casting ladle, the nonmetallic compound of other element is the chromated oxide that joins during the tapping of molten metal in the casting ladle; The content of manganese and chromium all improves 0.1% in the Finished Steel in order to make, in the material of the nonmetallic compound that comprises these elements chromated oxide with manganese-chromium than being that 1.1～1.2 amount adds, and as the aluminium of reductive agent with carbide of calcium with 1: the ratio of (2.9～3.2) adds.
9. method as claimed in claim 8, the wherein said raw material that comprises chromated oxide are the converter slag during medium carbon ferrochrome is produced.
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| RU2003107578 | 2003-03-20 | ||
| RU2003107578/02A RU2231559C1 (en) | 2003-03-20 | 2003-03-20 | Direct method for alloying steel with complex of elements |
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| KR100931870B1 (en) | 2005-04-13 | 2009-12-15 | 노키아 코포레이션 | Method, apparatus and system for effectively coding and decoding video data |
| CN100434556C (en) * | 2006-09-26 | 2008-11-19 | 山西太钢不锈钢股份有限公司 | Method for adding Mn into high Mn content stainless steel in smelting process |
| DE102007061062B4 (en) * | 2007-12-14 | 2012-08-02 | Peiner Träger GmbH | Process for producing a steel melt containing up to 30% manganese |
| KR101300740B1 (en) * | 2011-12-08 | 2013-08-28 | 주식회사 포스코 | Stabilizing method of ferro manganese dephosphorous slag |
| RU2577885C1 (en) * | 2014-12-22 | 2016-03-20 | Публичное акционерное общество "Северсталь" (ОАО "Северсталь") | Method for production of steel (versions) |
| WO2016172790A1 (en) * | 2015-04-26 | 2016-11-03 | Hatch Ltd. | Process and apparatus for producing high-manganese steels |
| CN109022840A (en) * | 2018-07-17 | 2018-12-18 | 北京科技大学 | A kind of secondary aluminium alloy microstructures Control method |
| CN115287390B (en) * | 2022-08-04 | 2023-08-22 | 重庆钢铁股份有限公司 | Method for producing low-phosphorus medium alloy steel by converter |
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| GB1508592A (en) | 1975-02-18 | 1978-04-26 | Nixon I | Manufacture of steel alloy steels and ferrous alloys |
| SU1044641A1 (en) * | 1982-06-18 | 1983-09-30 | Донецкий Ордена Трудового Красного Знамени Политехнический Институт | Method for alloying steel with manganese |
| DE3601337A1 (en) | 1986-01-16 | 1987-07-23 | Mannesmann Ag | METHOD FOR PRODUCING HIGH ALLOY STEELS IN THE OXYGEN BLOW CONVERTER |
| RU2096491C1 (en) | 1995-01-05 | 1997-11-20 | Государственный Обуховский завод | Steel foundry process |
| RU2096489C1 (en) | 1995-06-19 | 1997-11-20 | Акционерное общество открытого типа "НОСТА" (ОХМК) | Method of steel production in arc furnaces |
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| Title |
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| 采用锰矿对钢进行直接合金化. 文永才，董艳华等.钢铁钒钛，第19卷第3期. 1998 |
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| HK1090957A1 (en) | 2007-01-05 |
| UA73898C2 (en) | 2005-09-15 |
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| KR100802639B1 (en) | 2008-02-13 |
| AT502312A1 (en) | 2007-02-15 |
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| RU2231559C1 (en) | 2004-06-27 |
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