CN102199686B - Molten iron dephosphorization agent, and dephosphorization and desilication method for molten iron - Google Patents

Molten iron dephosphorization agent, and dephosphorization and desilication method for molten iron Download PDF

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CN102199686B
CN102199686B CN2010101316499A CN201010131649A CN102199686B CN 102199686 B CN102199686 B CN 102199686B CN 2010101316499 A CN2010101316499 A CN 2010101316499A CN 201010131649 A CN201010131649 A CN 201010131649A CN 102199686 B CN102199686 B CN 102199686B
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dephosphorization
molten iron
desiliconization
agent
iron
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CN102199686A (en
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郑皓宇
李安东
徐文杰
蒋兴元
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Baoshan Iron and Steel Co Ltd
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Abstract

The invention discloses a molten iron dephosphorization agent, and a dephosphorization and desilication method for molten iron. The molten iron dephosphorization agent is composed of the following components in parts by weight: 20-35 parts of acid-mixed iron oxide powder, 50-60 parts of dust-removed shot-blasting powder and 14-25 parts of dust-removed stainless steel smelting ash. The molten iron dephosphorization agent provided by the invention can be applied in all molten iron pretreatment processes, and has a strong dephosphorization function; simultaneously the molten iron dephosphorization agent contains solid oxides containing Cr and Ni, can slightly increase the Ni content in molten iron at a dephosphorization terminal by 5-8%, compared with original Ni content, and can reduce Ni addition amount during sequent smelting processes and lower production cost when used for smelting stainless steel; and all the raw materials for the molten iron dephosphorization agent are solid wastes containing Ni and Cr generated during stainless steel production processes of steel enterprises, and the wastes are recycled for molten iron dephosphorization, thus saving cost and reducing the emission of wastes.

Description

The method of molten iron dephosphorization agent and desiliconization of hot metal, dephosphorization
Technical field
The present invention relates to the method for a kind of molten iron dephosphorization agent and desiliconization of hot metal, dephosphorization.
Background technology
Along with the raising of people's living standard, the usage quantity of Stainless Steel Products is increasing, impels hot metal pretreatment desiliconization in the Iron And Steel Industry, dephosphorization operation to become the indispensable link of STEELMAKING PRODUCTION.
Because the desired phosphorus content of stainless steel finished product is all below 0.020%, and all process steps does not possess the dephosphorization function after the electric furnace, and this just requires in the hot metal pretreatment molten iron phosphorus content behind the dephosphorization less than 0.008% (the Low-phosphorus Steel kind requires phosphorus content≤0.006%).Comparatively speaking, blast furnace or smelting and rducing iron ores iron-smelting furnace (hereinafter to be referred as the COREX stove) silicon content generally 0.2%～0.6% and the fluctuation larger, and phosphorus content is basicly stable 0.080%～0.120%, brings larger pressure for hot metal pretreatment desiliconization and dephosphorization.
Under current economic environment, both guaranteed that stainless steel produced desired composition, reducing again operation production cost and the least possible generation waste is the key subject that stainless steel is produced.
Dephosphorization of molten iron is oxidising process, and in oxygen blast or oxygen supply process in iron liquid, silicon and manganese is prior to phosphorus oxidation, therefore, wants first desiliconization before the dephosphorization, only has after silicon drops under the certain level in the molten iron significantly oxidation of phosphorus.The conditions such as temperature, activity and additive are sequentially depended in the oxidation of carbon and phosphorus.Because iron is a large amount of as the solvent element, it is carrying out oxidation and two rightabout reactions of reduction simultaneously, plays the part of the role of transmitting oxygen.
Only have FeO, Fe in general desiliconization agent and the dephosphorizing agent 2O 3And Fe 3O 4Exist, and contain FeO, Fe in the oxide compound that each operation of stainless steel is discarded 2O 3, Fe 3O 4, Cr 2O 3, NiO, NiOCr 2O 3And FeOCr 2O 3, must exert an influence to desiliconization/dephosphorisation reaction.The driven force Epidemiological Analysis, Cr 2O 3And salt compounds CaCr 2O 4Fusing point all very high, the former is up to 2266 ℃, the latter also reaches 2090 ℃, these high-melting-point substances can make slag viscosity increase, and the dephosphorization of molten iron process is had serious disadvantageous effect.
Application for a patent for invention prospectus CN85101003A, the dephosphorization technology of a kind of low-phosphorous high chromium-stainless steel and ultralow phosphorus high chromium-stainless steel is disclosed, the method is the dephosphorization technology of low-phosphorous high chromium-stainless steel, sprays in the high-chromium stainless steel fluid in ladle or the ladle refining furnace as dephosphorizing agent with the pulvis of alkali or alkaline-earth metal and alloy thereof and carries out dephosphorization.Yet the method can be suitable for the dephosphorization of molten iron pre-treatment.
Application for a patent for invention prospectus CN1876857A, disclose a kind of take the method for molten iron as the main raw material smelting stainless steel, the method comprises (1) hot metal pretreatment a desiliconization of hot metal: being main iron scale pulvis blowing process in order to ferric oxide, is that the carrier gas powder monitor sprays in the molten iron with nitrogen; The desulfurization of b dephosphorization of molten iron: blowing and spraying method with pulvis, is that the dephosphorizing agent nitrogen of lime and fluorite is that the carrier gas powder monitor sprays in the molten iron with main component, carries out chemical reaction dephosphorization and desulfurization; (2) carry out preliminary decarburization and cr yield and alloying with top and bottom combined blown converter.
Application for a patent for invention prospectus CN1664127A discloses the method for a kind of dephosphorization of molten iron, desulfurization " what relate to mainly is that the form of flux with the sodium salt rafting is added in the molten iron.The described sodium salt flux that contains is yellow soda ash, sodium sulfate, also contains the materials such as sodium-chlor, caustic alkali in the flux.
Application for a patent for invention prospectus CN1372009A discloses a kind of molten iron, liquid steel dephosphorization agent, relates in a kind of ironmaking, the STEELMAKING PRODUCTION molten iron, liquid steel dephosphorization agent for reducing phosphorus content in the iron and steel.Dephosphorizing agent appoints calcium to form by ferric oxide, quickened lime, fluorine.
All there is a common shortcoming in related desiliconization agent, dephosphorizing agent and preparation thereof, the using method of above disclosed prior art, the preparation of desiliconization agent, dephosphorizing agent all needs additionally to purchase starting material, for example, alkali or alkaline-earth metal and alloy thereof, lime, fluorite, yellow soda ash, sodium sulfate, ferric oxide, fluorine are appointed calcium etc.Therefore must cause desiliconization of hot metal, dephosphorization production cost to rise.
Summary of the invention
For solving the deficiencies in the prior art, the present invention be intended to find out recycle that each stainless steel production link production of iron and steel enterprise takes out of contain chromium nickel solid waste, the molten iron dephosphorization agent and the corresponding dephosphorizing method that form by reprocessing and rational proportion.
One of technical problem to be solved by this invention provides a kind of molten iron dephosphorization agent.Molten iron dephosphorization agent of the present invention contains a certain amount of chromium nickel soild oxide, and that has recycled each operation in the iron and steel enterprise contains chromium nickel oxide solid waste.
Two of technical problem to be solved by this invention provides a kind of method of dephosphorization of molten iron.Dephosphorization rate reaches more than 90%, smelts low-phosphorous stainless purpose thereby reach.
Three of technical problem to be solved by this invention provides the method for a kind of desiliconization of hot metal and dephosphorization.The desiliconization rate reaches more than 70%, dephosphorization rate reaches more than 90%.Smelt low-phosphorous stainless purpose thereby reach.
For solving the problems of the technologies described above, the present invention is achieved through the following technical solutions:
A kind of molten iron dephosphorization agent is made of by weight following component:
20～35 parts of nitration mixture brown iron oxides;
50～60 parts of ball blast dust-removing powders;
14～25 parts of stainless steel-making dedusting ash.
Preferably, above-mentioned molten iron dephosphorization agent is made of by weight following component:
20～30 parts of nitration mixture brown iron oxides;
53～57 parts of ball blast dust-removing powders;
15～25 parts of stainless steel-making dedusting ash.
Described nitration mixture brown iron oxide by weight percentage, contains following component: FeO 28～32%; Fe 2O 315～20%; Cr 2O 32.0～2.5%; NiO 0.1～0.6%; SiO 2≤ 0.05%; S≤0.060%.Above-mentioned nitration mixture brown iron oxide is except containing cited component, and surplus is impurity.Usually surplus is CaO, MgO, MnO, H 2O, Fe 3O 4Oxidizing substance and composite oxides thereof Deng each chemical element.
Described ball blast dust-removing powder by weight percentage, contains following component: FeO 10～20%; Fe 2O 335～40%; Cr 2O 310～15%; NiO 2.0～3.5%; SiO 2≤ 0.05%; S≤0.060%.Above-mentioned ball blast dust-removing powder is except containing cited component, and surplus is impurity.Usually surplus is CaO, MgO, MnO, H 2O, Fe 3O 4Oxidizing substance and composite oxides thereof Deng each chemical element.
Described stainless steel-making dedusting ash by weight percentage, contains following component: FeO 6～12%; Fe 2O 318～27%; Cr 2O 38～12%; NiO 1.0～1.5%; SiO 2≤ 0.04%; S≤0.060%.Above-mentioned stainless steel-making dedusting ash is except containing cited component, and surplus is impurity.Usually surplus is CaO, MgO, MnO, H 2O, Fe 3O 4Oxidizing substance and composite oxides thereof Deng each chemical element.
The invention also discloses a kind of method of dephosphorization of molten iron, adopt molten iron dephosphorization agent to carry out dephosphorization, wherein said dephosphorizing agent adopts aforesaid molten iron dephosphorization agent.
Described dephosphorization method for molten iron is torpedo Molten Iron Transportation tank injection dephosphorization method or iron ladle injection dephosphorization method.
The present invention further discloses the method for a kind of desiliconization of hot metal and dephosphorization, comprises desiliconization of hot metal step and dephosphorization of molten iron step,
Described desiliconization of hot metal step adopts the desiliconization of hot metal agent to carry out desiliconization, and this desiliconization of hot metal agent is made of by weight following component: 10～20 parts of nitration mixture brown iron oxides; 15～25 parts of ball blast dust-removing powders; 10～20 parts of stainless steel-making dedusting ash; 40～60 parts on rolling iron oxide squama.
Preferably, described desiliconization of hot metal agent is made of by weight following component: 14～16 parts of nitration mixture brown iron oxides; 18～22 parts of ball blast dust-removing powders; 14～16 parts of stainless steel-making dedusting ash; 48～52 parts on rolling iron oxide squama.
The dephosphorization of molten iron step adopts molten iron dephosphorization agent to carry out dephosphorization, and this dephosphorizing agent adopts aforesaid molten iron dephosphorization agent.
Preferably, described desiliconization of hot metal method is mixed desiliconization method or the dephosphorizing station winding-up desiliconization method of rushing of molten iron ladle pouring; Described dephosphorization method for molten iron is torpedo Molten Iron Transportation tank injection dephosphorization method or iron ladle injection dephosphorization method.
Concrete, in technique scheme:
Described nitration mixture brown iron oxide, enter the nitration mixture regeneration site and process for the cold rolling mill coil of strip is mixing with spent acid after the pickling at the Surface Fe oxide compound under the coiled sheet surface acid-washing in acid cleaning process, wherein spent acid becomes regenerating acid after treatment for the pre-pickling of coil of strip, and the soild oxide that is settled out just forms the nitration mixture brown iron oxide.Its conventional output flow process is specifically referring to Fig. 1.
In brief, namely in the cold rolling mill production process of steel coil, the solid waste of collecting from the nitration mixture regeneration site is one of raw material that will use required for the present invention nitration mixture brown iron oxide.
Described ball blast dust-removing powder, for the cold rolling mill coil of strip finish rolling and through annealing after, the surface oxidation iron laden dust under the coil of strip surface treatment that in carrying out coil of strip descaling surfaces and Shot Blasting process, produces and surface oxidation abrasive grit dirt; Wherein iron oxide dust is that scale breading operation dust-removal system is collected in the scale breading treating processes dust, oxidation abrasive grit dirt are the grain dirt of the ball blast operation larger particles that dust-removal system is collected in the Shot Blasting process, these two kinds of dedusting products reclaim through a recovery system, the soild oxide general designation ball blast dust-removing powder that reclaims.Its conventional output flow process is specifically referring to Fig. 1.
In brief, namely in the cold rolling mill production process of steel coil, the solid waste iron oxide dust of collecting respectively from ball blast operation, scale breading operation is one of raw material that will use required for the present invention ball blast dust-removing powder.
Described stainless steel-making dedusting ash is the dedusting product of each smelting procedure of stainless steel-making factory.The stainless steel smelting operation mainly comprises the operations such as ultra high power ac arc furnace (hereinafter to be referred as EAF) mother liquor of stainless steel electric melting furnace, top side Argon oxygen decarbonizing furnace (hereinafter to be referred as AOD) top side Argon oxygen decarbonizing furnace, vacuum-oxygen decarbonizing a refining unit (hereinafter to be referred as VOD) equipment for vacuum refining; Also be applicable to the stainless steel smelting operations such as top bottom blowing argon oxygen decarburizing furnace (hereinafter to be referred as KOBMS) top bottom blowing argon oxygen decarburizing furnace, ladle refining furnace (hereinafter to be referred as LF) ladle refining furnace, vacuum decarburization a refining unit (hereinafter to be referred as VD) a refining unit.Its dedusting product ∑ Fe reaches 30%～35%, and in the dedusting ash oxidizing substance mainly with Fe 2O 3Form exist and (contain Fe 2O 3〉=20%); And the dedusting product of these stainless steel operations contains 0.8%～1.4% nickel, can increase nickel by trace in molten iron after being prepared into desiliconization of hot metal agent of the present invention, has certain recycling to be worth for stainless steel with the dephosphorization molten iron.Its conventional output flow process is specifically referring to Fig. 2.
Described rolling iron oxide squama, for hot rolling mill before slab rough rolling before de-scaling treatment process and the finish rolling de-scaling treatment process steel billet is being rolled the solid waste oxygen compound of output in the front surface treating processes, by hot fine rolling unit surface descaling device (hereinafter to be referred as FSB) the de-scaling station output before descaling device (hereinafter to be referred as HSB) the de-scaling station, surface of the hot rolling roughing mill group before the roughing and the finish rolling and after the settling tank precipitation, reclaim; The rolling iron oxide squama that rolling iron oxide squama raw material described in the present invention can adopt stainless steel coil of strip rolling iron oxide squama, carbon steel coil of strip rolling iron oxide squama, carbon steel and stainless steel reinforced concrete to roll, the iron scale that the iron scale that the stainless steel continuous casting steel slab surface that also is applicable to adopt the continuous casting settling tank to reclaim produces, carbon steel slab surface produce.Its conventional output flow process is specifically referring to Fig. 3.
Because the rolling iron oxide squama results from settling tank, moisture content is very high, generally 5%～20%, distribution of particle sizes wide range and be entrained with certain foreign material, therefore when using scale oxide, drying or baking processing and particle screen selecting preferably advance first.
The present invention adopt nitration mixture brown iron oxide, ball blast dust-removing powder, stainless steel-making factory steel-making dedusting ash, these 4 each operations of stainless steel of hot rolling mill scale oxide discarded contain chromium, nickel soild oxide as the starting material of desiliconization agent, dephosphorizing agent, its theoretical foundation is as follows:
Table 1 be depicted as each operation of stainless steel discarded contain chromium, nickel soild oxide main component, it mainly (contains FeO, Fe by ∑ Fe 2O 3), SiO 2, Cr 2O 3, NiO forms; From the curve of Fig. 4, can clearly judge NiO, FeO and Cr 2O 3Si in the successively oxidation molten iron, therefore from thermodynamic (al) viewpoint analysis, the soild oxide that contains chromium nickel can be used for desiliconization of hot metal, and recyclable nickel and a small amount of chromium.
Table 1: each operation waste composition (unit: the quality percentage composition) of stainless steel
The name of an article FeO Fe 2O 3 Cr 2O 3 NiO SiO 2 S
The nitration mixture brown iron oxide 28～32 15～20 2.0～2.5 0.1～0.6 ≤0.05 ≤0.060
The ball blast dust-removing powder 10～20 35～40 10～15 2.0～3.5 ≤0.05 ≤0.060
The stainless steel-making dedusting ash 6～12 18～27 8.0～12 1.0～1.5 ≤0.04 ≤0.060
The rolling iron oxide squama 38～45 7～12 2.0～5.0 1.2～1.8 1.0～1.5 ≤0.060
Nitration mixture brown iron oxide in the table 1, ball blast dust-removing powder, stainless steel-making dedusting ash and rolling iron oxide squama are except containing above-mentioned FeO, Fe 2O 3, Cr 2O 3, NiO, SiO 2Outside the components such as S, also contain CaO, MgO, MnO, H 2O, Fe 3O 4Oxidizing substance and composite oxides thereof Deng each chemical element.
It is complicated many that actual dephosphorization of molten iron is wanted.As being the positive and negative degree analyzing that the standard of oxide compound generates the free enthalpy increment from the Ellingham figure of Fig. 4 only, only have NiO can with the oxidation molten iron in phosphorus reaction, and FeO can not, Cr 2O 3More can not.But know from process for making, in the situation that additive or fixing agent (such as CaO) are arranged, FeO can dephosphorization.This is because CaO and P 2O 5Reaction generates stable 3CaOP 2O 5Or 4CaOP 2O 5Thereby, greatly reduced P in the slag 2O 5Activity.P is being arranged under the condition of lime 2O 5Dephosphorization need be judged with the expression formula of following reaction and corresponding free enthalpy increment:
3(CaO)+2[P]+5/3(Cr 2O 3)＝(3CaO·P 2O 5)+10/3[Cr]
4(CaO)+2[P]+5/3(Cr 2O 3)＝(4CaO·P 2O 5)+10/3[Cr]
ΔG θ 31＝419763-153.63T＝-RTlnk 31
Wherein: K 31=a (3CaO P2O5)A [Cr] 10/3/ { a (CaO) 3A (Cr2O3) 5/3A [P] 2}
At 1300 ℃ (1573K), K 31=1.21 * 10 -6
K 31Very little, Cr is described 2O 3Dephosphorisation reaction be difficult to carry out.
In addition, contain Cr in chromium/nickel soild oxide 2O 3Also may with lime in CaO react, consume lime, its reaction equation is as follows:
(Cr 2O 3)+(CaO)＝(CaCr 2O 4)
ΔG 0 32＝-2399730+467.145T
And: CaCr 2O 4Very stable, can not carry out dephosphorization under oxidizing atmosphereLin Fenpeibi, can find out from following formula:
5/3(CaCr 2O 4)+4/3(CaO)+2[P]＝(3CaO·P 2O 5)+10/3[Cr]
And:
5/3(CaCr 2O 4)+7/3(CaO)+2[P]＝(4CaO·P 2O 5)+10/3[Cr]
ΔG θ 34＝4419313-624.945T ＝-RT lnK 34
Equally: calculate the K at 1300 ℃ 34=5.1 * 10 -11
K 34Less, CaO and Cr are described 2O 3Generate CaCr after the reaction 2O 4Lost dephosphorization fully active.
Therefore, from the thermodynamics viewpoint analysis, contain the Cr in the soild oxide of chromium nickel 2O 3In dephosphorization of molten iron without positive effect.
The driven force Epidemiological Analysis, Cr 2O 3And salt compounds CaCr 2O 4Fusing point all very high, the former is up to 2266 ℃, the latter also reaches 2090 ℃, these high-melting-point substances can make slag become sticky, and the dephosphorization of molten iron process is had certain disadvantageous effect.
Dynamic analysis by desiliconization of hot metal, dephosphorization knows, the melting of desiliconization, dephosphorizing agent directly affects the speed of reaction.That is, fusing point is low, changes the slag condition good, and the speed of desiliconization, dephosphorisation reaction is fast.And contain the adding of the soild oxide (following referred to as CNFe) of chromium nickel, will inevitably the melting of original desiliconization, dephosphorizing agent be exerted an influence, therefore the melting of Ni and Cr contained desiliconization, dephosphorizing agent is studied.Result of study such as Fig. 5, Fig. 6, shown in Figure 7.
By the curve display of Fig. 8, Fig. 9 and Figure 10, the softening temperature of limy desiliconization agent, hemisphere point temperature and fine melt temperature all raise gradually along with the increase of CNFe substitution rate.Its softening temperature, hemisphere point temperature and CNFe substitution rate are approximated to linear relationship; And weight break point appears in its fine melt temperature at CNFe substitution rate 75% place, surpasses that the fine melt temperature of desiliconization agent sharply raises behind 75% substitution rate.When substitution rate surpasses after 75%, sub-melting phenomenon appears, and this is by Cr in the desiliconization agent 2O 3, CaCr 2O 4And the high-melting-point material such as NiO causes.
Along with the increase of CNFe substitution rate, the softening temperature of the dephosphorizing agent of high oxidation iron level, hemisphere point temperature and fine melt temperature variation are unusually remarkable, and its fine melt temperature has raise and spent 300 more.When the substitution rate of the soild oxide that contains chromium nickel surpasses after 40%, the melting region of same dephosphorizing agent (i.e. temperature range from incipient melting to fine melt) also reaches more than 250 ℃.Fig. 8, Fig. 9 and Figure 10 curve have shown that the various temperature of fusion of two kinds of dephosphorizing agents are with the changing conditions of CNFe substitution rate increase and different variation tendencies.
The softening temperature of the dephosphorizing agent of high oxidation iron level, hemisphere point temperature and fine melt temperature all raise with the increase of CNFe substitution rate, and when the CNFe substitution rate reached 20～25%, the fine melt temperature of dephosphorizing agent sharply raise, and melting region is elongated and sub-melting phenomenon occurs.For the dephosphorizing agent of middle iron oxide content, its softening temperature, hemisphere point temperature and fine melt temperature are with the increase of CNFe substitution rate, and lifting is not obvious generally.All present slow decreasing trend in last stage three kinds of temperature, when the CNFe substitution rate reaches after 40%, along with the increase of replacement rate, temperature recovery and sub-melting phenomenon do not occur.Can find out from the melting variation tendency of dephosphorizing agent, ferriferous oxide shared proportioning in the dephosphorizing agent raw material is larger, and the soild oxide that then contains chromium nickel is larger on the impact of dephosphorizing agent melting on the substitution rate of sintering breeze.
According to above-mentioned laboratory results and correlation theory research conclusion, we carry out the dephosphorizing agent proportioning take " middle iron oxide content " as the dephosphorizing agent matching principle: adopt CaO:40～50%; CaF 2: 4～8%; Fe 2O 3: the proportioning of 45～50% (wherein: contain chromium nickel soild oxide CNFe:20～25%) is carried out the iron ladle injection dephosphorization, has all reached dephosphorization target value ([P] in laboratory test and type approval test Terminal point≤ 0.010%).Substitute Fe and contain chromium nickel soild oxide CNFe 2O 3Substitution rate reach 47～51%.Therefore it is feasible substituting 50% soild oxide that does not contain chromium nickel with the soild oxide that contains chromium nickel.
According to above-mentioned result of study, the present invention has developed a kind of iron oxide content moderate the desiliconization of hot metal agent and the dephosphorizing agent that contain chromium/nickel soild oxide, recycle each operation in the iron and steel enterprise discarded contain the method that chromium, nickel soild oxide carry out desiliconization of hot metal/phosphorus agent preparation and use.The characteristics of this desiliconization agent, dephosphorizing agent be to adapt to blast furnace before the hot metal pretreatment or COREX stove silicon content of hot metal the fluctuation of [Si]=0.2～0.8% (traditional desiliconization/dephosphorizing agent require [Si] initial maximum≤0.3%), when carrying out desiliconization/dephosphorizing pretreatment; The desiliconization rate reaches more than 70%, dephosphorization rate reaches more than 90%.Smelt low-phosphorous stainless purpose thereby reach.
The preparation method of desiliconization agent of the present invention, dephosphorizing agent is:
(1) the nitration mixture brown iron oxide is collected;
(2) the ball blast dust-removing powder is collected;
(3) the stainless steel-making dedusting ash is collected;
(4) the rolling iron oxide squama is collected;
(5) preparation of desiliconization of hot metal agent:
As shown in figure 11, above-mentioned 4 kinds of materials enter the preparatory phase of desiliconization agent after raw material is prepared, at first by the mixing of weighing of desiliconization agent proportion scale, then toast, preferably control requires water content≤3%, carrying out sufficient mixing stirs again, be formed into the product desiliconization agent behind the mixing, be transported to the desiliconization of hot metal place with strength conveying trough tank car suction tank car, such as molten iron ladle pouring station,, carry out desiliconization of hot metal and use to the desiliconization feed bin with the pneumatic conveying mode material loading.
Best, this finished product desiliconization agent quality is carried out following control: water content≤3% when 1) finished product molten iron desiliconization agent puts in storage after the processing; 2) mixing stirs fully, and the desiliconization of hot metal agent is put in storage without piling up demixing phenomenon; 3) every batch of desiliconization agent turnout is produced by the actual demand of desiliconization of hot metal production capacity, put in storage rear storage time≤36 hour of desiliconization agent; 4) the strength conveying trough tank car for the desiliconization agent transportation must keep clean, and forbids to use the vehicle loading, transportation and the material loading that once loaded the explosive materials such as magnesium powder, calcium carbide powder.
Obviously, simply, also can, with these four solid waste of nitration mixture brown iron oxide, ball blast dust-removing powder, stainless steel-making dedusting ash and rolling iron oxide squama of collecting, oven dry moisture, ratio takes by weighing above-mentioned four solid waste by weight, mechanical disintegration, mix, oven dry moisture can make desiliconization of hot metal agent of the present invention.
(6) preparation of dephosphorizing agent:
As shown in figure 12, three kinds of materials such as above-mentioned nitration mixture brown iron oxide, ball blast dust-removing powder, stainless steel-making dedusting ash enter the preparatory phase of dephosphorizing agent after raw material is prepared, at first by the mixing of weighing of dephosphorizing agent proportion scale, then toast (requiring moisture content≤1%), carrying out sufficient mixing stirs again, be formed into the product dephosphorizing agent behind the mixing, be transported to dephosphorization of molten iron place (molten iron injection dephosphorization station) with strength conveying trough tank car suction tank car,, carry out dephosphorization of molten iron and use to the dephosphorization feed bin with the pneumatic conveying mode material loading.
To finished product dephosphorizing agent specification of quality: 1) finished product dephosphorizing agent moisture content≤1% that puts in storage after the processing.2) mixing stirs fully, and dephosphorizing agent puts in storage without piling up demixing phenomenon.3) every batch of dephosphorizing agent turnout is produced by the actual demand of dephosphorization of molten iron production capacity, put in storage rear storage time≤24 hour of dephosphorizing agent.4) the strength conveying trough tank car for the dephosphorizing agent transportation must keep clean, and forbids to use the vehicle loading, transportation and the material loading that once loaded the explosive materials such as magnesium powder, calcium carbide powder.
Obviously, simply, also can, with these three solid waste of nitration mixture brown iron oxide, ball blast dust-removing powder and stainless steel-making dedusting ash of collecting, oven dry moisture, ratio takes by weighing above-mentioned three solid waste by weight, mechanical disintegration, mix, oven dry moisture can make molten iron dephosphorization agent of the present invention.
The invention also discloses a kind of dephosphorization method for molten iron, can adopt the general technique of the industry to carry out, such as torpedo Molten Iron Transportation tank injection dephosphorization method, iron ladle injection dephosphorization method etc., its improvements are, the molten iron dephosphorization agent that adopts is made of by weight following component:
20～35 parts of nitration mixture brown iron oxides;
50～60 parts of ball blast dust-removing powders;
14～25 parts of stainless steel-making dedusting ash.
For better carrying out dephosphorization of molten iron, before the dephosphorization step, can also carry out first desiliconization of hot metal.Therefore, the present invention further discloses the method for a kind of desiliconization of hot metal, dephosphorization, comprises desiliconization of hot metal step and dephosphorization of molten iron step,
Described desiliconization of hot metal step adopts the desiliconization of hot metal agent to carry out desiliconization, and this desiliconization of hot metal agent is made of by weight following component:
10～20 parts of nitration mixture brown iron oxides;
15～25 parts of ball blast dust-removing powders;
10～20 parts of stainless steel-making dedusting ash;
40～60 parts on rolling iron oxide squama.
Described dephosphorization of molten iron step adopts above-mentioned molten iron dephosphorization agent to carry out dephosphorization.
The addition of the technique of specifically not described in the present invention,, desiliconization agent, dephosphorizing agent and equipment etc. all are the conventional uses of the industry.
The advantage of technical solution of the present invention is mainly reflected in following several respects:
The present invention is applied to all hot metal pre process procedures, except having very strong desiliconization and dephosphorization function, also has the function of improving molten iron reaction oxidizing atmosphere, desiliconization of hot metal, the desired oxidisability condition of dephosphorization technology, homogenizing slag condition and thermodynamical reaction condition can be provided, reach the purpose that reduces silicon and phosphorus in the molten iron; And all raw materials of this prescription be use that each stainless steel production link production of iron and steel enterprise takes out of contain chromium nickel solid waste, be a kind of resource be easy to get, easy to produce and use, with low cost and be conducive to nickel resources and reclaim again and the desiliconization of hot metal that promotes environmental protection, dephosphorizing agent.Simultaneously waste has been carried out reclaiming reprocessing utilization, saved cost and reduced the quantity discharged of waste.
In the present invention, use to contain chromium nickel soild oxide, can make dephosphorization terminal point molten iron nickel content slightly increase by 5%～8% on the basis of original nickel content, increasing the nickel amount is 0.001～0.003%; For smelting stainless steel, can corresponding minimizing after the nickel amount of allocating in the operation smelting process, reduce production costs.
Description of drawings
Fig. 1 is the production scheme of stainless steel-making dedusting ash output;
Fig. 2 is the production scheme of rolling iron oxide squama output;
Fig. 3 is the production scheme of nitration mixture brown iron oxide, ball blast dust-removing powder output;
Fig. 4 is that the standard generation free enthalpy increment of oxide compound varies with temperature Ellingham figure;
Fig. 5 is that the substitution rate of CNFe is on the figure that affects of desiliconization agent softening temperature;
Fig. 6 is that the substitution rate of CNFe is on the figure that affects of desiliconization agent hemisphere point temperature;
Fig. 7 is that the substitution rate of CNFe is on the figure that affects of desiliconization agent fine melt temperature;
Fig. 8 is that the substitution rate of CNFe is on the figure that affects of dephosphorizing agent softening temperature;
Fig. 9 is that the substitution rate of CNFe is on the figure that affects of two kinds of dephosphorizing agent hemisphere point temperature;
Figure 10 is that the substitution rate of CNFe is on the figure that affects of two kinds of dephosphorizing agent fine melt temperature;
Figure 11 is the preparation flow figure of desiliconization agent of the present invention;
Figure 12 is the preparation flow figure of dephosphorizing agent of the present invention.
Embodiment
Raw material is collected
(1) the nitration mixture brown iron oxide is collected:
Reclaim after the nitration mixture brown iron oxide drying that cold rolling mill nitration mixture regeneration site spent acid processing postprecipitation goes out and put in storage, be transported to the desiliconization agent processing space by strength conveying trough tank car suction tank car; Press desiliconization agent proportion scale and the pre-mixing of ball blast dust-removing powder, enter storage bin after the mixing for subsequent use.
Pre-mixing requires to mix fully, and two material are planted without piling up demixing phenomenon; Little and tap density is low because of nitration mixture brown iron oxide granularity, must consider the airborne dust loss amount approximately 3% in the nitration mixture brown iron oxide preparation process in the preparation process.
(2) the ball blast dust-removing powder is collected:
The ball blast dust-removing powder of output in cold rolling mill scale breading operation and the ball blast operation dust removal process is reclaimed by dust-removal cloth-bag and to enter the dust storehouse, by truck transport to the desiliconization agent processing space; Press desiliconization agent proportion scale and the pre-mixing of nitration mixture brown iron oxide, enter storage bin after the mixing for subsequent use.
Pre-mixing requires to mix fully, and two material are planted without piling up demixing phenomenon.
(3) the stainless steel-making dedusting ash is collected:
The stainless steel-making dedusting ash derives from the operations such as stainless steel-making EAF, AOD, VOD, also divided by EAF electrostatic precipitator, AOD dry collector and VOD bag-type dust machine output in dust removal process respectively to be stored in different dust collection ash silos, be transported to the desiliconization agent processing space by strength conveying trough tank car suction tank car; Use first 40 order mesh screens to carry out screening out of adulterant, then carry out the pre-mixing of stainless steel-making dedusting ash, as one batch only for the steel-making dedusting ash of a certain operation output does not then need pre-mixing, carry out drying treatment behind the mixing, put in storage after the drying for subsequent use.
Mix and require two or more dissimilar stainless steel-making dedusting ash to mix the obvious demixing phenomenon of rear nothing accumulation.And because the lower characteristic of nickel content in its dedusting ash in the VOD vacuum-treat process, in principle in 1 batch VOD dedusting ash usage ratio be controlled at be lower than steel-making dedusting ash total amount 30% in.
(4) the rolling iron oxide squama is collected:
Hot rolling mill is the rolling iron oxide squama of de-scaling treatment process output before slab rough rolling and before the finish rolling, after scale oxide settling tank precipitation, by truck transport to the desiliconization agent processing space; Use first 40 order mesh screens to carry out mishmash and screen out, then carry out drying and baking processing, make its moisture content less than 5%; Carry out again the graded particie screening, the 1st road is 40 order particle screen selectings for the screening of≤5mm coarse particles, the 2nd road for≤3mm particle screen selecting, the 3rd road, the small-particle warehouse entry that meets the service requirements of preparing burden is for subsequent use, the macrobead thing carries out milled processed to meeting the batching service requirements, and the particle requirement after the screening sees Table 2.
Table 2
Granularity ＞5mm ＞4mm 1mm≤particle≤3mm ＜100μm
Ratio, % 0 ≤0.5 ≤10 ≤10
Embodiment 1
The preparation of desiliconization of hot metal agent
Technical process as shown in figure 11, above-mentioned 4 kinds of materials after preparing, raw material are entered the preparatory phase of desiliconization agent, at first in the mixing of weighing of each feed proportioning ratio of desiliconization agent in the 1 corresponding hurdle of embodiment in the table 3, then toast, preferably control requires water content≤3%, carrying out sufficient mixing stirs again, be formed into the product desiliconization agent behind the mixing, be transported to the desiliconization of hot metal place with strength conveying trough tank car suction tank car, such as molten iron ladle pouring station,, carry out desiliconization of hot metal and use to the desiliconization feed bin with the pneumatic conveying mode material loading.
This finished product desiliconization agent quality is carried out following control:
Water content≤3% when 1) finished product molten iron desiliconization agent puts in storage after the processing.2) mixing stirs fully, and the desiliconization of hot metal agent is put in storage without piling up demixing phenomenon.3) every batch of desiliconization agent turnout is produced by the actual demand of desiliconization of hot metal production capacity, put in storage rear storage time≤36 hour of desiliconization agent.4) the strength conveying trough tank car for the desiliconization agent transportation must keep clean, and forbids to use the vehicle loading, transportation and the material loading that once loaded the explosive materials such as magnesium powder, calcium carbide powder.Can obtain desiliconization of hot metal agent of the present invention.
Further, the physical and chemical index of the embodiment of the invention 1 desiliconization of hot metal agent is detected, concrete data see table 4 for details.
Embodiment 2
The preparation of desiliconization of hot metal agent
Technical process is weighed in each feed proportioning ratio of desiliconization agent in the 2 corresponding hurdles of embodiment in the table 3 as shown in figure 11, adopts the identical method of embodiment 1, can prepare desiliconization of hot metal agent of the present invention.
Further, the physical and chemical index of the embodiment of the invention 2 desiliconization of hot metal agent is detected, concrete data see table 4 for details.
Embodiment 3
The preparation of desiliconization of hot metal agent
With these four solid waste of nitration mixture brown iron oxide, ball blast dust-removing powder, stainless steel-making dedusting ash and rolling iron oxide squama of collecting, oven dry moisture, take by weighing above-mentioned four solid waste in corresponding ratio in the 3 corresponding hurdles of embodiment in the table 3, mechanical disintegration, mix, oven dry moisture can make desiliconization of hot metal agent of the present invention.
Further, the physical and chemical index of the embodiment of the invention 3 desiliconization of hot metal agent is detected, concrete data see table 4 for details.
Table 3: desiliconization of hot metal agent finished product proportioning table
The nitration mixture brown iron oxide The ball blast dust-removing powder The stainless steel-making dedusting ash The rolling iron oxide squama
Embodiment 1 15 weight parts 20 weight parts 15 weight parts 50 weight parts
Embodiment 2 10 weight parts 20 weight parts 10 weight parts 60 weight parts
Embodiment
3 20 weight parts 20 weight parts 20 weight parts 40 weight parts
Table 4: the concrete physical and chemical index data sheet of desiliconization of hot metal agent
∑Fe FeO Fe 2O 3 SiO 2 S P Cr 2O 3 NiO
Embodiment 1 55.1 53.2 1.8 0.81 0.043 0.085 6.52 1.63
Embodiment 2 59.6 58.4 1.0 0.89 0.055 0.101 7.68 1.78
Embodiment 3 50.9 49.3 1.4 0.63 0.038 0.074 4.01 1.45
Embodiment 4
Desiliconization of hot metal
Adopt that molten iron ladle pouring is mixed to be rushed the desiliconization method molten iron is carried out desiliconization, wherein used desiliconization agent is the prepared desiliconization of hot metal agent of the embodiment of the invention 1.
Molten iron ladle pouring is mixed to rush the desiliconization method at fish torpedo ladle during to the iron ladle hot metal charging, desiliconization agent is dropped into the molten iron streamer, utilize the dynamic conditions melting solid desiliconization agent of the thermodynamic condition of high temperature liquid iron and molten iron streamer and make it and molten iron generation chemical reaction, remove the silicon in the molten iron.The method is the general a kind of desiliconization of hot metal method of the industry.
Desiliconization of hot metal agent add-on is by following static parameter, and is as shown in table 5.
Table 5: the mixed desiliconization method of rushing of molten iron ladle pouring is used desiliconization of hot metal agent add-on static parameter list
Figure GSA00000063584600141
Technology point:
A, require uniform feeding in molten iron, itself and molten iron are fully reacted, avoid splash; In B, the tank switching operation, when iron ladle seethes fierceness, should reduce simultaneously the adding speed of tank switching speed and desiliconization material; When bits will overflow the tank mouth, stop immediately tank switching and add material.In the time of C, molten iron temperature T≤1300 ℃, forbid this desiliconization of hot metal agent.
The used desiliconization agent of the present embodiment is the prepared desiliconization of hot metal agent of the embodiment of the invention 1, carries out altogether the utilization of 5 tank molten iron; The add-on of molten iron condition, treatment capacity and desiliconization agent, consumption figures, terminal point [Si], desiliconization rate see following table 6 for details.
The add-on of molten iron condition, treatment capacity and desiliconization agent, consumption figures, terminal point [Si], desiliconization rate table look-up among table 6: the embodiment 4
Figure GSA00000063584600142
Embodiment 5
Desiliconization of hot metal
Adopt dephosphorizing station winding-up desiliconization method that molten iron is carried out desiliconization, wherein used desiliconization agent is the prepared desiliconization of hot metal agent of the embodiment of the invention 1.
Dephosphorizing station winding-up desiliconization method is a kind of at jet the stage by stage molten iron pretreatment method of desiliconization and injection dephosphorization of same station.In the desiliconization stage, mainly be to utilize spray gun to spray into the solid desiliconization agent to the molten iron deep, in iron ladle, produce strong mixing with the kinetic energy of high pressure carrier gas (ordinary method use nitrogen), the process temperature of processing with oxygen gun blowing control desiliconization of hot metal.The thermodynamic condition that the chemical reaction heat that utilizes the heat energy of high temperature liquid iron and oxygen gun blowing to produce brings utilizes the dynamic conditions melting solid desiliconization agent that the N2 gas agitating produces and makes it and molten iron generation chemical reaction, removes [Si] in the molten iron.After finishing desiliconization, after removing desiliconization slag, carry out again dephosphorization of molten iron.The method is the general a kind of desiliconization of hot metal method of the industry.
Desiliconization of hot metal agent add-on is by following static parameter, and is as shown in table 7.
Table 7: dephosphorizing station winding-up desiliconization method is used desiliconization of hot metal agent add-on static parameter list
Technology point:
In A, the winding-up/stirring desiliconization process, when molten iron level seethes fierceness, should reduce injecting velocity and suspend reinforced; When bits will overflow the tank mouth, stop immediately processing.B, maximum input amount regulation: the maximum input amount of desiliconization≤30kg/t iron; C, during in molten iron temperature T≤1200 ℃, forbidding desiliconization material.D, oxygen use regulation: the desiliconization maximum oxygen of standing amount is restricted to 75% of conventional FeO blowing oxygen quantity.
The used desiliconization of hot metal agent of the present embodiment is the prepared desiliconization of hot metal agent of the embodiment of the invention 1, has carried out altogether the utilization of 5 tank molten iron; The add-on of molten iron condition, treatment capacity and desiliconization agent, consumption figures, terminal point [Si], desiliconization rate see following table 8 for details.
The add-on of molten iron condition, treatment capacity and desiliconization agent, consumption figures, terminal point [Si], desiliconization rate table look-up among table 8: the embodiment 5
Embodiment 6
Desiliconization of hot metal
Adopt that molten iron ladle pouring is mixed to be rushed the desiliconization method molten iron is carried out desiliconization, wherein used desiliconization agent is the prepared desiliconization of hot metal agent of the embodiment of the invention 2.The add-on static parameter list that molten iron ladle pouring is mixed to rush desiliconization method and technology point thereof, employing desiliconization of hot metal agent of the present invention is with embodiment 4, and concrete data see Table 5.
The used desiliconization agent of the present embodiment is the prepared desiliconization of hot metal agent of the embodiment of the invention 2, carries out altogether the utilization of 8 tank molten iron; The add-on of molten iron condition, treatment capacity and desiliconization agent, consumption figures, terminal point [Si], desiliconization rate see following table 9 for details.
The add-on of molten iron condition, treatment capacity and desiliconization agent, consumption figures, terminal point [Si], desiliconization rate table look-up among table 9: the embodiment 6
Figure GSA00000063584600162
Figure GSA00000063584600171
Embodiment 7
Desiliconization of hot metal
Adopt dephosphorizing station winding-up desiliconization method that molten iron is carried out desiliconization, wherein used desiliconization agent is the prepared desiliconization of hot metal agent of the embodiment of the invention 2.The add-on static parameter list of dephosphorizing station winding-up desiliconization method and technology point thereof, employing desiliconization of hot metal agent of the present invention is with embodiment 5, and concrete data see Table 7.
The used desiliconization agent of the present embodiment is the prepared desiliconization of hot metal agent of the embodiment of the invention 2, has carried out altogether the utilization of 8 tank molten iron; See following table 10 for details.
The add-on of molten iron condition, treatment capacity and desiliconization agent, consumption figures, terminal point [Si], desiliconization rate table look-up among table 10: the embodiment 7
Figure GSA00000063584600172
Embodiment 8
Desiliconization of hot metal
Adopt that molten iron ladle pouring is mixed to be rushed the desiliconization method molten iron is carried out desiliconization, wherein used desiliconization agent is the prepared desiliconization of hot metal agent of the embodiment of the invention 3.
Molten iron ladle pouring is mixed to rush the add-on static parameter list of desiliconization method and technology point thereof, employing desiliconization of hot metal agent of the present invention with embodiment 4.Concrete data see Table 5.
The used desiliconization agent of the present embodiment is the prepared desiliconization of hot metal agent of the embodiment of the invention 3, has carried out altogether the utilization of 4 tank molten iron; The add-on of molten iron condition, treatment capacity and desiliconization agent, consumption figures, terminal point [Si], desiliconization rate see following table 11 for details.
The add-on of molten iron condition, treatment capacity and desiliconization agent, consumption figures, terminal point [Si], desiliconization rate table look-up among table 11: the embodiment 8
Embodiment 9
Desiliconization of hot metal
Adopt dephosphorizing station winding-up desiliconization method that molten iron is carried out desiliconization, wherein used desiliconization agent is the prepared desiliconization of hot metal agent of the embodiment of the invention 3.The add-on static parameter list of dephosphorizing station winding-up desiliconization method and technology point thereof, employing desiliconization of hot metal agent of the present invention is with embodiment 5.Concrete data see Table 7.
The used desiliconization agent of the present embodiment is the prepared desiliconization of hot metal agent of the embodiment of the invention 3, has carried out altogether the utilization of 5 tank molten iron; The add-on of molten iron condition, treatment capacity and desiliconization agent, consumption figures, terminal point [Si], desiliconization rate see following table 12 for details.
The add-on of molten iron condition, treatment capacity and desiliconization agent, consumption figures, terminal point [Si], desiliconization rate table look-up among table 12: the embodiment 9
From the concrete data of embodiment 4～9 as seen, use desiliconization of hot metal agent of the present invention, carried out practical application in stainless steel-making factory, result of use is good.
Obtain from actual service condition combined data, adopt desiliconization of hot metal agent of the present invention, in the listed standard deviation scope of starting material design proportioning, (press respectively the maximum value of main oxides composition, minimum value, mean value) carrying out actual proportioning uses, under the processing parameter and technological standard of design, within containing chromium/nickel soild oxide desiliconization agent add-on setting range, rush desiliconization molten iron ladle pouring station is mixed, desiliconization of hot metal rate under the injecting station desilication process condition of dephosphorization of molten iron station has reached the preset standard requirement, also reach the consumption level of the every auxiliary material when using conventional desiliconization agent, seen table 13 for details.
Table 13: the consumption level of the every auxiliary material when using molten iron of the present invention to take off agent
Figure GSA00000063584600192
The actual proof of using adopts the design's desiliconization of hot metal agent that safety in production and environment protection are had no adverse effect.
Embodiment 10
The preparation of molten iron dephosphorization agent
As shown in figure 12, three kinds of materials such as above-mentioned nitration mixture brown iron oxide, ball blast dust-removing powder, stainless steel-making dedusting ash enter the preparatory phase of dephosphorizing agent after raw material is prepared,
At first in the mixing of weighing of each feed proportioning ratio of dephosphorizing agent in the 10 corresponding hurdles of embodiment in the table 14, then toast (requiring moisture content≤1%), carrying out sufficient mixing stirs again, be formed into the product dephosphorizing agent behind the mixing, be transported to dephosphorization of molten iron place (molten iron injection dephosphorization station) with strength conveying trough tank car suction tank car,, carry out dephosphorization of molten iron and use to the dephosphorization feed bin with the pneumatic conveying mode material loading.
To finished product dephosphorizing agent specification of quality:
1) finished product dephosphorizing agent moisture content≤1%2 of putting in storage after the processing) mixing stirs fully, dephosphorizing agent puts in storage without piling up demixing phenomenon 3) every batch of dephosphorizing agent turnout produces by the actual demand of dephosphorization of molten iron production capacity, dephosphorizing agent rear storage time≤24 hours 4 of putting in storage) the strength conveying trough tank car that is used for the dephosphorizing agent transportation must keep clean, and forbids to use the vehicle loading, transportation and the material loading that once loaded the explosive materials such as magnesium powder, calcium carbide powder.Can obtain molten iron dephosphorization agent of the present invention.
Physical and chemical index to the embodiment of the invention 10 molten iron dephosphorization agents detects, and concrete data see table 15 for details.
Table 14: molten iron dephosphorization agent finished product proportioning table
The nitration mixture brown iron oxide The ball blast dust-removing powder The stainless steel-making dedusting ash
Embodiment
10 30 weight parts 55 weight parts 15 weight parts
Embodiment 11 20 weight parts 60 weight parts 20 weight parts
Embodiment 12 25 weight parts 50 weight parts 25 weight parts
Table 15: the concrete physical and chemical index data sheet of molten iron dephosphorization agent
∑Fe Fe 2O 3 SiO 2 S P Cr 2O 3 NiO
Embodiment 10 56.1 54.7 0.25 0.043 0.085 6.52 1.63
Embodiment 11 59.2 57.5 0.29 0.055 0.101 6.52 1.63
Embodiment 12 51.4 50.2 0.21 0.038 0.074 6.52 1.63
Embodiment 11
The preparation of molten iron dephosphorization agent
Technical process is weighed in each feed proportioning ratio of dephosphorizing agent in the 11 corresponding hurdles of embodiment in the table 14 as shown in figure 12, adopts the identical method of embodiment 10, can prepare molten iron dephosphorization agent of the present invention.
Physical and chemical index to the embodiment of the invention 11 molten iron dephosphorization agents detects, and concrete data see table 15 for details.
Embodiment 12
The preparation of molten iron dephosphorization agent
With these three solid waste of nitration mixture brown iron oxide, ball blast dust-removing powder and stainless steel-making dedusting ash of collecting, oven dry moisture, weigh in each feed proportioning ratio of dephosphorizing agent in the 12 corresponding hurdles of embodiment in the table 14, mechanical disintegration, mix, oven dry moisture can make molten iron dephosphorization agent of the present invention.
Physical and chemical index to the embodiment of the invention 12 molten iron dephosphorization agents detects, and concrete data see table 15 for details.
Embodiment 13
Dephosphorization of molten iron
Adopt torpedo Molten Iron Transportation tank injection dephosphorization method that molten iron is carried out dephosphorization, wherein used dephosphorizing agent is the embodiment of the invention 10,11,12 prepared molten iron dephosphorization agents.
Torpedo Molten Iron Transportation tank injection dephosphorization method is a kind of molten iron pretreatment method that carries out injection dephosphorization in torpedo Molten Iron Transportation tank.Be the general a kind of dephosphorization of molten iron method of the industry.
Torpedo Molten Iron Transportation tank injection dephosphorization method is a kind of molten iron pretreatment method that the molten iron of silicon content≤0.30% is carried out injection dephosphorization.Mainly be to utilize the oblique rifle that dusts to spray into the solid dephosphorizing agent in the deep of molten iron in the tank.Utilize the kinetic energy of high pressure carrier gas (ordinary method use nitrogen) in iron ladle, to produce the carrying out that stirs the promotion dephosphorisation reaction; The thermodynamic condition that utilizes the heat energy of high temperature liquid iron to bring utilizes the dynamic conditions melting solid desiliconization agent that the N2 gas agitating produces and makes it and molten iron generation chemical reaction, removes [P] in the molten iron.After finishing dephosphorization, skim at fish torpedo ladle and to convert again iron after the station removes dephosphorized slag.The method is the general a kind of molten iron winding-up pretreatment process of the industry.
The molten iron dephosphorization agent add-on is by following static parameter, and is shown in table 16.
Table 16
Figure GSA00000063584600221
Implemented by powder injection in torpedo dephosphorization technology parameter list is shown in table 17.
Table 17
Technology point:
In A, the injection dephosphorization process, when tank mouth molten iron level seethes fierceness, should reduce injecting velocity; When finding that having scum to overflow the tank mouth should stop winding-up immediately.B, maximum input amount regulation :≤33kg/t iron; C, during in molten iron temperature T≤1420 ℃, ban use of this dephosphorizing agent to carry out the dephosphorization operation.
The used molten iron desquamation agent of the present embodiment is the embodiment of the invention 10,11,12 prepared molten iron dephosphorization agents, has carried out altogether the utilization of 7 tank molten iron; The add-on of molten iron condition, treatment capacity and dephosphorizing agent, consumption figures, terminal point [P], dephosphorization rate see following table 18 for details.
The add-on of molten iron condition, treatment capacity and dephosphorizing agent, consumption figures, terminal point [P], dephosphorization rate table look-up among table 18: the embodiment 13
Figure GSA00000063584600231
Embodiment 14
Dephosphorization of molten iron
Adopt iron ladle injection dephosphorization method that molten iron is carried out dephosphorization, wherein used dephosphorizing agent is the prepared molten iron dephosphorization agent of the embodiment of the invention 11.
Iron ladle injection dephosphorization method is a kind of molten iron pretreatment method that carries out injection dephosphorization in the open type iron ladle.Be the general a kind of dephosphorization of molten iron method of the industry.
Dephosphorizing station injection dephosphorization method is a kind of at jet the stage by stage molten iron pretreatment method of desiliconization and injection dephosphorization of same station.In the dephosphorization stage, mainly be that molten iron to silicon content of hot metal after the desiliconization≤0.15% carries out dephosphorization treatment, utilize spray gun to spray into the solid desiliconization agent to the molten iron deep, kinetic energy with high pressure carrier gas (ordinary method use nitrogen) produces strong mixing in iron ladle, with the process temperature of oxygen gun blowing control desiliconization of hot metal processing.The thermodynamic condition that the chemical reaction heat that utilizes the heat energy of high temperature liquid iron and oxygen gun blowing to produce brings utilizes the dynamic conditions melting solid desiliconization agent that the N2 gas agitating produces and makes it and molten iron generation chemical reaction, removes [P] in the molten iron.After finishing dephosphorization, remove dephosphorized slag.The method is the general a kind of dephosphorization method for molten iron of the industry.
The molten iron dephosphorization agent add-on is by following static parameter, and is shown in table 19.
Table 19
Figure GSA00000063584600241
Iron ladle injection dephosphorization process parameter table is shown in table 20, table 21.
Table 20
Figure GSA00000063584600242
Figure GSA00000063584600251
Table 21
[%Si] initial value % 0.05％ 0.07％ 0.09％ 0.12％ 0.15％
Amount of oxygen (Nm 3/t) 5.0～6.0 6.0～6.5 6.5～6.8 6.8～7.2 7.2～7.5
The blowing oxygen time (min) 10～14 14～16 16～20 20～24 24～27
CaO/CaF 2(kg/t) 2.1～2.3 3.2～3.5 5.4～5.9 7.5～8.3 9.6～10.6
Technology point:
In A, the injection dephosphorization process, when molten iron level seethes fierceness, should reduce injecting velocity and suspend reinforced; When bits will overflow the tank mouth, stop immediately processing.B, maximum input amount regulation: the maximum input amount of dephosphorization≤35kg/t iron C, during in molten iron temperature T≤1200 ℃, forbid this dephosphorizing agent and carry out the dephosphorization operation.D, oxygen usage quantity regulation: dephosphorization maximum oxygen amount is restricted to 85% of conventional Fe2O3 blowing oxygen quantity.
The used molten iron desquamation agent of the present embodiment is the prepared molten iron dephosphorization agent of the embodiment of the invention 11, has carried out altogether the utilization of 7 stove molten iron; The add-on of molten iron condition, treatment capacity and dephosphorizing agent, consumption figures, terminal point [P], dephosphorization rate see following table 22 for details.
The add-on of molten iron condition, treatment capacity and dephosphorizing agent, consumption figures, terminal point [P], dephosphorization rate table look-up among table 22: the embodiment 14
Figure GSA00000063584600261
Embodiment 15
Dephosphorization of molten iron
Adopt iron ladle injection dephosphorization method that molten iron is carried out dephosphorization, wherein used dephosphorizing agent is the prepared molten iron dephosphorization agent of the embodiment of the invention 12.
Iron ladle injection dephosphorization process parameter table is shown in table 20, table 21.
The used molten iron desquamation agent of the present embodiment is the prepared molten iron dephosphorization agent of the embodiment of the invention 12, has carried out altogether the utilization of 8 stove molten iron; The add-on of molten iron condition, treatment capacity and dephosphorizing agent, consumption figures, terminal point [P], dephosphorization rate see following table 23 for details.
The add-on of molten iron condition, treatment capacity and dephosphorizing agent, consumption figures, terminal point [P], dephosphorization rate table look-up among table 23: the embodiment 15
Figure GSA00000063584600271
Figure GSA00000063584600281
Embodiment 16
Adopt the iron ladle blowing process to carrying out dephosphorization treatment after the desiliconization of molten iron elder generation, wherein used desiliconization agent is the prepared desiliconization of hot metal agent of the embodiment of the invention 2; Wherein used dephosphorizing agent is the prepared molten iron dephosphorization agent of the embodiment of the invention 10.
Iron ladle winding-up desiliconization method and injection dephosphorization method are a kind of molten iron pretreatment methods that carries out injection dephosphorization in the open type iron ladle.Be the general a kind of dephosphorization of molten iron method of the industry.
Dephosphorizing station winding-up desiliconization method and injection dephosphorization method are a kind of at jet the stage by stage molten iron pretreatment method of desiliconization and injection dephosphorization of same station.In the desiliconization stage, mainly be to utilize spray gun to spray into the solid desiliconization agent to the molten iron deep, in iron ladle, produce strong mixing with the kinetic energy of high pressure carrier gas (ordinary method use nitrogen), the process temperature of processing with oxygen gun blowing control desiliconization of hot metal.The thermodynamic condition that the chemical reaction heat that utilizes the heat energy of high temperature liquid iron and oxygen gun blowing to produce brings utilizes the dynamic conditions melting solid desiliconization agent that the N2 gas agitating produces and makes it and molten iron generation chemical reaction, removes [Si] in the molten iron.After finishing desiliconization, after removing desiliconization slag, carry out again dephosphorization of molten iron.The method is the general a kind of desiliconization of hot metal method of the industry.In the dephosphorization stage, mainly be that molten iron to silicon content of hot metal after the desiliconization≤0.15% carries out dephosphorization treatment, utilize spray gun to spray into the solid desiliconization agent to the molten iron deep, kinetic energy with high pressure carrier gas (ordinary method use nitrogen) produces strong mixing in iron ladle, with the process temperature of oxygen gun blowing control desiliconization of hot metal processing.The thermodynamic condition that the chemical reaction heat that utilizes the heat energy of high temperature liquid iron and oxygen gun blowing to produce brings utilizes the dynamic conditions melting solid desiliconization agent that the N2 gas agitating produces and makes it and molten iron generation chemical reaction, removes [P] in the molten iron.After finishing dephosphorization, remove dephosphorized slag.The method is the general a kind of dephosphorization method for molten iron of the industry.
Desiliconization of hot metal agent add-on static parameter is as shown in table 7.
Iron ladle injection dephosphorization process parameter table is shown in table 20, table 21.
The used desiliconization of hot metal agent of the present embodiment is the prepared desiliconization of hot metal agent of the embodiment of the invention 2, and the used molten iron desquamation agent of the present embodiment is the prepared molten iron dephosphorization agent of the embodiment of the invention 12, has carried out altogether the utilization of 5 stove molten iron; The add-on of molten iron condition, treatment capacity and desiliconization agent, dephosphorizing agent, consumption figures, terminal point [P], desiliconization rate, dephosphorization rate see following table 24 for details.
From the concrete data of embodiment 13～16 as seen, use molten iron dephosphorization agent of the present invention, carried out practical application in stainless steel-making factory, result of use is good.
Obtain from actual service condition combined data, adopt molten iron dephosphorization agent of the present invention, in the listed standard deviation scope of starting material design proportioning, (press respectively the maximum value of main oxides composition, minimum value, mean value) carrying out actual proportioning uses, under the processing parameter and technological standard of design, within containing chromium/nickel soild oxide desiliconization agent add-on setting range, at the implemented by powder injection in torpedo dephosphorization, the injecting station desiliconization of dephosphorization of molten iron station, dephosphorization of molten iron rate under the injection dephosphorization processing condition of dephosphorization of molten iron station has reached the preset standard requirement, also reach the consumption level of the every auxiliary material when using conventional dephosphorizing agent, seen table 25 for details, table 26.
Table 25: the consumption level of the every auxiliary material when the implemented by powder injection in torpedo dephosphorization uses molten iron dephosphorization agent of the present invention
Figure GSA00000063584600291
Table 26: the consumption level of the every auxiliary material when the iron ladle injection dephosphorization uses molten iron dephosphorization agent of the present invention
Figure GSA00000063584600292
The actual proof of using adopts the design's molten iron dephosphorization agent that safety in production and environment protection are had no adverse effect.
Figure GSA00000063584600301

Claims (7)

1. a molten iron dephosphorization agent is characterized in that, is comprised of by weight following component:
20～35 parts of nitration mixture brown iron oxides;
50～60 parts of ball blast dust-removing powders;
14～25 parts of stainless steel-making dedusting ash;
Wherein,
Described nitration mixture brown iron oxide, by weight percentage, contain following component:
FeO 28～32%；
Fe 2O 3 15～20%；
Cr 2O 3 2.0～2.5%；
NiO 0.1～0.6%；
SiO 2 ≤0.05%；
S ≤0.060%；
Described ball blast dust-removing powder, by weight percentage, contain following component:
FeO 10～20%；
Fe 2O 3 35～40%；
Cr 2O 3 10～15%；
NiO 2.0～3.5%；
SiO 2 ≤0.05%；
S ≤0.060%；
Described stainless steel-making dedusting ash, by weight percentage, contain following component:
FeO 6～12%；
Fe 2O 3 18～27%；
Cr 2O 3 8～12%；
NiO 1.0～1.5%；
SiO 2 ≤0.04%；
S ≤0.060%。
2. molten iron dephosphorization agent as claimed in claim 1 is characterized in that, is comprised of by weight following component:
20～30 parts of nitration mixture brown iron oxides;
53～57 parts of ball blast dust-removing powders;
15～25 parts of stainless steel-making dedusting ash.
3. the method for a dephosphorization of molten iron adopts molten iron dephosphorization agent to carry out dephosphorization, it is characterized in that, described dephosphorizing agent is claim 1 or 2 described molten iron dephosphorization agents.
4. the method for dephosphorization of molten iron as claimed in claim 3 is characterized in that, described dephosphorization method for molten iron is torpedo Molten Iron Transportation tank injection dephosphorization method or iron ladle injection dephosphorization method.
5. the method for a desiliconization of hot metal and dephosphorization comprises desiliconization of hot metal step and dephosphorization of molten iron step, it is characterized in that,
Described desiliconization of hot metal step adopts the desiliconization of hot metal agent to carry out desiliconization, and described desiliconization of hot metal agent is made of by weight following component:
10～20 parts of nitration mixture brown iron oxides;
15～25 parts of ball blast dust-removing powders;
10～20 parts of stainless steel-making dedusting ash;
40～60 parts on rolling iron oxide squama;
Wherein,
Described nitration mixture brown iron oxide, by weight percentage, contain following component:
FeO 28～32%；
Fe 2O 3 15～20%；
Cr 2O 3 2.0～2.5%；
NiO 0.1～0.6%；
SiO 2 ≤0.05%；
S ≤0.060%；
Described ball blast dust-removing powder, by weight percentage, contain following component:
FeO 10～20%；
Fe 2O 3 35～40%；
Cr 2O 3 10～15%；
NiO 2.0～3.5%；
SiO 2 ≤0.05%；
S ≤0.060%；
Described stainless steel-making dedusting ash, by weight percentage, contain following component:
FeO 6～12%；
Fe 2O 3 18～27%；
Cr 2O 3 8～12%；
NiO 1.0～1.5%；
SiO 2 ≤0.04%；
S ≤0.060%；
Described dephosphorization of molten iron step adopts molten iron dephosphorization agent to carry out dephosphorization, and described dephosphorizing agent is claim 1 or 2 described molten iron dephosphorization agents.
6. the method for desiliconization of hot metal as claimed in claim 5 and dephosphorization, it is characterized in that: described desiliconization of hot metal agent is made of by weight following component:
14～16 parts of nitration mixture brown iron oxides;
18～22 parts of ball blast dust-removing powders;
14～16 parts of stainless steel-making dedusting ash;
48～52 parts on rolling iron oxide squama.
7. the method for desiliconization of hot metal as claimed in claim 5 and dephosphorization is characterized in that:
Described desiliconization of hot metal method is mixed desiliconization method or the dephosphorizing station winding-up desiliconization method of rushing of molten iron ladle pouring;
Described dephosphorization method for molten iron is torpedo Molten Iron Transportation tank injection dephosphorization method or iron ladle injection dephosphorization method.
CN2010101316499A 2010-03-24 2010-03-24 Molten iron dephosphorization agent, and dephosphorization and desilication method for molten iron Expired - Fee Related CN102199686B (en)

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CN106967864A (en) * 2016-01-14 2017-07-21 武汉科技大学 A kind of production method of novel liquid steel dephosphorization slag former
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