CN106676233A - Pre-fused compound dephosphorizer, preparation method of pre-fused compound dephosphorizer and method for smelting ultralow phosphorous steel - Google Patents
Pre-fused compound dephosphorizer, preparation method of pre-fused compound dephosphorizer and method for smelting ultralow phosphorous steel Download PDFInfo
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Abstract
The invention relates to the field of smelt low-phosphorous steel, in particular to pre-fused compound dephosphorizer. The pre-fused compound dephosphorizer is composed of, by weight percent, 30%-60% of a mixture of iron sesquioxide (Fe2O3) and ferrous oxide (FeO), 20%-50% of calcium oxide (CaO), 0%-10% of aluminum oxide (Al2O3), 0%-10% of silicon dioxide (SiO2), 0%-10% of magnesium oxide (MgO), 5%-30% of calcium fluoride (CaF2) and unavoidable impurities. The invention also relates to a preparation method of the pre-fused compound dephosphorizer. The invention further relates to a method for smelting ultralow phosphorous steel. The dephosphorizing rate of the pre-fused compound dephosphorizer can reach 80% or above, and the phosphorous content in liquid steel can be controlled within 0.003%.
Description
Technical field
The present invention relates to the field of smelting of Low-phosphorus Steel, relates in particular to a kind of pre-melted type compound dephosphorization agent and preparation method thereof.The invention further relates to a kind of method for smelting ultra-low phosphoretic steel.
Background technology
In the smelting process of iron and steel, phosphorus needs to be controlled by usually as harmful element.Because segregation of the phosphorus in steel makes steel toughness be deteriorated than more serious, " cold short " phenomenon is produced, especially under cryogenic, it is easier to occur " cold short ".
In order under the conditions of low-temperature cold, there is no cold short phenomenon in use or working steel products, the phosphorus in steel typically should be controlled below 0.012%.And the phosphorus in clean steel and ultra-low phosphoretic steel must be controlled below 0.005%.
To reach this purpose, most steel mill adopts " double slag process ", i.e., go in another converter after taking a block converter by dephosphorization of molten iron using slag making twice or " two-step method " in converter smelting and smelted.The method of this two kinds reduction phosphorus, the duration of heat is long, can only carry out in the case where converter smelting production has and has more than needed.
Another kind of method is that molten iron is pre-processed, i.e., molten steel is carried out " three take off " using torpedo hot metal mixer car and ladle（Desiliconization, dephosphorization, desulfurization）Process, this technique is widely used at present in each steel mill.But its weak point be need to, investment many with equipment is big, processing procedure unit consumption is high, temperature drop is big, and because the molten iron temperature after " three take off " is low, greatly reduce the steel scrap amount added during converter smelting.
Therefore, in order to produce low-phosphorous, ultra-low phosphoretic steel, conventional converter smelting method can not meet requirement of these steel grades to phosphorus, so the require study new Dephosphorising agent of exploitation and corresponding dephosphorization method, so as to realize producing ultra-low phosphoretic steel.
China national Department of Intellectual Property disclosed entitled " Dephosphorising agent for converter and preparation method thereof " on December 6th, 2006（CN 1873031A）Application for a patent for invention, wherein it is public come described Dephosphorising agent for converter be by iron oxide, calcium oxide, alundum (Al2O3), silica, magnesia at a temperature of 1000 DEG C ~ 1550 DEG C fritting gained, and in the addition of converter smelting early stage carry out slag making dephosphorization.Though the Dephosphorising agent is produced using the method for high temperature fritting, its every component is the higher material of fusing point, and not only fusing point is higher for gained Dephosphorising agent, and viscosity is larger after slagging.In addition, after using the Dephosphorising agent, phosphorus content is 0.004% ~ 0.010% in steel after blow off, it is impossible to reach the demand smelted in ultra-low phosphoretic steel.
Additionally, China national Department of Intellectual Property disclosed entitled " process of manufacturing ultra-low phosphoretic steel with outside-stove refining dephosphorization of liquid steel " on December 24th, 2008（CN 101328529A）Application for a patent for invention, it is disclosed that a kind of micro alloyed steel, high-carbon steel and special steel produce the process of ultra-low phosphoretic steel, including converter tapping, first dephosphorization, deep dephosphorization, skim, the step such as heating stirring, deoxidation alloying refining treatment, continuous casting.Though the method can control the phosphorus content after dephosphorization below 0.0030%, to need through going out dephosphorization, whole dephosphorization dephosphorization operation twice, and also need to carry out deep dephosphorization using the mode of feeding core-spun yarn, complex process is relatively costly.
The content of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art part, there is provided a kind of pre-melted type compound dephosphorization agent.The compound dephosphorization agent is mainly used for pneumatic steelmaking, is added in ladle with steel stream in converter tapping process, to play the effect of deep dephosphorization to molten steel.
The present invention also aims to provide a kind of preparation method of above-mentioned pre-melted type compound dephosphorization agent.
The present invention also aims to provide a kind of method of smelting ultra-low phosphoretic steel, the method is included in converter tapping process and above-mentioned pre-melted type compound dephosphorization agent is added in ladle with steel stream, so as to reach the purpose for smelting ultra-low phosphoretic steel.
According to a first aspect of the present invention, it is related to a kind of pre-melted type compound dephosphorization agent, and the pre-melted type compound dephosphorization agent is made up of by weight percentage following components and inevitable impurity：Di-iron trioxide（Fe2O3）And ferrous oxide（FeO）Mixture：30%~60%；Calcium oxide（CaO）：20%~50%；Alundum (Al2O3)（Al2O3）：0~10%；Silica（SiO2）：0~10%；Magnesia（MgO）：0~10%；Calcirm-fluoride（CaF2）：5%~30%.
Due to being limited by raw material etc., " di-iron trioxide（Fe2O3）" and " ferrous oxide（FeO）" be with mixture in the form of and exist.Wherein, in the mixture, di-iron trioxide（Fe2O3）And ferrous oxide（FeO）Between percentage composition be：Di-iron trioxide（Fe2O3）For 0.5%-99.5%, ferrous oxide（FeO）For 99.5%-0.5%.
According to a preferred embodiment of a first aspect of the present invention, the pre-melted type compound dephosphorization agent is consisted of：Di-iron trioxide（Fe2O3）And ferrous oxide（FeO）Mixture：40%~50%；Calcium oxide（CaO）：30%~45%；Alundum (Al2O3)（Al2O3）：0~8%；Silica（SiO2）：0~8%；Magnesia（MgO）：0~8%；Calcirm-fluoride（CaF2）：5%~25%.
According to more one preferred embodiment of a first aspect of the present invention, the pre-melted type compound dephosphorization agent is consisted of：Di-iron trioxide（Fe2O3）And ferrous oxide（FeO）Mixture 40%；Calcium oxide（CaO）45%；Alundum (Al2O3)（Al2O3）4%；Silica（SiO2）3%；Magnesia（MgO）2%；Calcirm-fluoride（CaF2）6%.
According to more one preferred embodiment of a first aspect of the present invention, the pre-melted type compound dephosphorization agent is consisted of：Di-iron trioxide（Fe2O3）And ferrous oxide（FeO）Mixture 45%；Calcium oxide（CaO）40%；Alundum (Al2O3)（Al2O3）2%；Silica（SiO2）3%；Magnesia（MgO）2%；Calcirm-fluoride（CaF2）8%.
According to more one preferred embodiment of a first aspect of the present invention, the pre-melted type compound dephosphorization agent is consisted of：Di-iron trioxide（Fe2O3）And ferrous oxide（FeO）Mixture 50%；Calcium oxide（CaO）35%；Alundum (Al2O3)（Al2O3）4%；Silica（SiO2）3%；Magnesia（MgO）2%；Calcirm-fluoride（CaF2）6%.
According to more one preferred embodiment of a first aspect of the present invention, the pre-melted type compound dephosphorization agent is consisted of：Di-iron trioxide（Fe2O3）And ferrous oxide（FeO）Mixture 55%；Calcium oxide（CaO）25%；Alundum (Al2O3)（Al2O3）4%；Silica（SiO2）3%；Magnesia（MgO）2%；Calcirm-fluoride（CaF2）11%.
According to a second aspect of the present invention, it is related to a kind of method for preparing above-mentioned pre-melted type compound dephosphorization agent, and it comprises the following steps：
（1）Above-mentioned component is crushed, is mixed and/or pelletizing,
（2）The fusing in 1100 DEG C ~ 1600 DEG C of temperature range by the product of gained；
（3）Jing after cooling, crushing, pre-melted type compound dephosphorization agent is obtained；
Wherein, resulting pre-melted type compound dephosphorization agent granularity is 1 ~ 30mm.
According to a third aspect of the present invention, it is related to a kind of method of smelting ultra-low phosphoretic steel, and the method is mainly included the following steps that：
（1）Converter tapping：After converter smelting terminates, the end phosphorus content of converter is controlled below 0.02%, tapping temperature is controlled at 1560 DEG C ~ 1660 DEG C, deoxidation treatment is not carried out to molten steel in tapping process, and processed using pushing off the slag in tapping process；
（2）Converter tapping deep dephosphorization：Flow to steel in converter tapping process and above-mentioned pre-melted type compound dephosphorization agent is added in ladle, ladle is transported into Argon station after the completion of tapping, Argon stirring is carried out to molten steel；
（3）Skim：The slag on the molten steel surface after dephosphorization treatment is removed using Cinder Machine, is subsequently adding ladle covering agent；
（4）Deoxidation alloying refining treatment：Ladle is transported into refining station, deoxidation, alloying, temperature adjustment process is carried out.
（5）Continuous casting：Cast using whole process protection.
According to a preferred embodiment of a third aspect of the present invention, wherein described pushing off the slag is processed to be realized using any one mode in floating plug, skimming ball, slag retaining cone or valve plate slag stopping.
According to a preferred embodiment of a third aspect of the present invention, wherein wherein（2）In individual step, described pre-melted type Dephosphorising agent is homogeneously added into ladle to tapping end by tapping, and with mixed with molten steel slag is washed into, and carries out phosphorus deep removal.
According to a preferred embodiment of a third aspect of the present invention, wherein described pre-melted type compound dephosphorization agent consumption is 3 ~ 10 kgs/tonne of molten steel,
Pre-melted type compound dephosphorization agent component of the present invention is reasonable, basicity is high, fusing point is low, dephosphorization thermodynamic condition is good, and add in converter tapping process, mixed punching effect is played with molten steel, being capable of rapid melting slag making dephosphorization, dynamic conditions is outstanding, after tapping dephosphorization terminates, scarfing cinder process is carried out using vacuum dreg-sucking machine or mechanical Cinder Machine, ensure that molten steel occurs in the refining process in later stage without rephosphorization phenomenon, dephosphorization rate can be such that phosphorus content in molten steel controls below 0.003% up to more than 80%.
Secondly, pre-melted type compound dephosphorization agent of the present invention can stably control phosphorus content in molten steel.Its in use effect substantially, it is stable, it can be ensured that and/or improve steel quality, reduce smelting cost, and its preparation process is simple, beneficial to using, operation, transport and store.
Additionally, the method that deep dephosphorization of the present invention smelts ultra-low phosphoretic steel is mainly used in converter tapping.The method is in converter tapping process by pre-melted type compound dephosphorization agent as steel stream is added in ladle, so as to play a part of deep dephosphorization to molten steel, described compound dephosphorization agent has very strong dephosphorizing capacity, can stably control phosphorus content in molten steel, and after dephosphorization through skimming, the production technology such as deoxidation alloying, continuous casting.Described method effect is obvious, stable, it can be ensured that and/or steel quality is improved, smelting cost is reduced, and the method is simple to operate, and the production for being conducive to steel mill is controlled.
Specific embodiment
Embodiment
1
（1）Prepare pre-melted type compound dephosphorization agent：
By di-iron trioxide（Fe2O3）And ferrous oxide（FeO）Mixture 400kg；Calcium oxide（CaO）450kg；Alundum (Al2O3)（Al2O3）40kg；Silica（SiO2）30kg；Magnesia（MgO）20kg；Calcirm-fluoride（CaF2）60kg melts after crushing, mixing and/or pelletizing at a high temperature of 1100 DEG C ~ 1600 DEG C, and the converter tapping pre-melted type compound dephosphorization agent 950kg for obtaining that granularity is 10 ~ 20mm is processed Jing after cooling is broken.
（2）Smelt ultra-low phosphoretic steel：
Tapping Temperature of Bof is controlled between 1560 DEG C ~ 1660 DEG C, and phosphorus content is controlled below 0.02% during tapping, is carried out pushing off the slag using non-deoxidation, slide plate pushing off the slag technology and is processed tapping；Start to tapping to terminate uniformly to add pre-melted type compound dephosphorization agent in ladle from converter tapping; wherein the amount of molten steel is 105 tons; the amount that pre-melted type compound dephosphorization agent is added is 550kg; Dephosphorising agent carries out Argon stirring after adding to molten steel; Argon carries out process of skimming after terminating, and in the backward molten steel of end of skimming ladle covering agent is added, and subsequently ladle is transported to external refining station carries out deoxidation alloying process; after molten steel reaches steel grade requirement, full guard casting is carried out.
Embodiment
2
（1）Prepare pre-melted type compound dephosphorization agent：
By di-iron trioxide（Fe2O3）And ferrous oxide（FeO）Mixture 450kg；Calcium oxide（CaO）400kg；Alundum (Al2O3)（Al2O3）20kg；Silica（SiO2）30kg；Magnesia（MgO）20kg；Calcirm-fluoride（CaF2）80kg melts after crushing, mixing and/or pelletizing at a high temperature of 1100 DEG C ~ 1600 DEG C, and the converter tapping pre-melted type compound dephosphorization agent 960kg for obtaining that granularity is 15 ~ 20mm is processed Jing after cooling is broken.
（2）Smelt ultra-low phosphoretic steel：
Tapping Temperature of Bof is controlled between 1560 DEG C ~ 1660 DEG C, and phosphorus content is controlled below 0.02% during tapping, is carried out pushing off the slag using non-deoxidation, slide plate pushing off the slag technology and is processed tapping；Start to tapping to terminate uniformly to add pre-melted type compound dephosphorization agent in ladle from converter tapping; wherein the amount of molten steel is 104 tons; the amount that pre-melted type compound dephosphorization agent is added is 500kg; Dephosphorising agent carries out Argon stirring after adding to molten steel; Argon carries out process of skimming after terminating, and in the backward molten steel of end of skimming ladle covering agent is added, and subsequently ladle is transported to external refining station carries out deoxidation alloying process; after molten steel reaches steel grade requirement, full guard casting is carried out.
Embodiment
3
（1）Prepare pre-melted type compound dephosphorization agent：
By di-iron trioxide（Fe2O3）And ferrous oxide（FeO）Mixture 500kg；Calcium oxide（CaO）350kg；Alundum (Al2O3)（Al2O3）40kg；Silica（SiO2）30kg；Magnesia（MgO）20kg；Calcirm-fluoride（CaF2）60kg melts after crushing, mixing and/or pelletizing at a high temperature of 1100 DEG C ~ 1600 DEG C, and the converter tapping pre-melted type compound dephosphorization agent 950kg for obtaining that granularity is 12 ~ 18mm is processed Jing after cooling is broken.
（2）Smelt ultra-low phosphoretic steel：
Tapping Temperature of Bof is controlled between 1560 DEG C ~ 1660 DEG C, and phosphorus content is controlled below 0.02% during tapping, is carried out pushing off the slag using non-deoxidation, slide plate pushing off the slag technology and is processed tapping；Start to tapping to terminate uniformly to add pre-melted type compound dephosphorization agent in ladle from converter tapping; wherein the amount of molten steel is 102 tons; the amount that pre-melted type compound dephosphorization agent is added is 450kg; Dephosphorising agent carries out Argon stirring after adding to molten steel; Argon carries out process of skimming after terminating, and in the backward molten steel of end of skimming ladle covering agent is added, and subsequently ladle is transported to external refining station carries out deoxidation alloying process; after molten steel reaches steel grade requirement, full guard casting is carried out.
Embodiment
4
（1）Prepare pre-melted type compound dephosphorization agent：
By di-iron trioxide（Fe2O3）And ferrous oxide（FeO）Mixture 550kg；Calcium oxide（CaO）250kg；Alundum (Al2O3)（Al2O3）40kg；Silica（SiO2）30kg；Magnesia（MgO）20kg；Calcirm-fluoride（CaF2）110kg melts after crushing, mixing and/or pelletizing at a high temperature of 1100 DEG C ~ 1600 DEG C, and the converter tapping pre-melted type compound dephosphorization agent 950kg for obtaining that granularity is 15 ~ 18mm is processed Jing after cooling is broken.
（2）Smelt ultra-low phosphoretic steel：
Tapping Temperature of Bof is controlled between 1560 DEG C ~ 1660 DEG C, and phosphorus content is controlled below 0.02% during tapping, is carried out pushing off the slag using non-deoxidation, slide plate pushing off the slag technology and is processed tapping；Start to tapping to terminate uniformly to add pre-melted type compound dephosphorization agent in ladle from converter tapping; wherein the amount of molten steel is 105 tons; the amount that pre-melted type compound dephosphorization agent is added is 450kg; Dephosphorising agent carries out Argon stirring after adding to molten steel; Argon carries out process of skimming after terminating, and in the backward molten steel of end of skimming ladle covering agent is added, and subsequently ladle is transported to external refining station carries out deoxidation alloying process; after molten steel reaches steel grade requirement, full guard casting is carried out.
The process for being used for converter tapping deep dephosphorization using the above embodiment of the present invention has carried out smelting test, and according to the difference of tapping end phosphorus content, the difference of dephosphorization amount, more than 80%, phosphorus content is controlled 0.0030% or less dephosphorization amount in molten steel.
Shown in concrete effect following table：
The present invention is been described by by above-mentioned related embodiment, but above-described embodiment only implements the example of the present invention.It must be noted that, it has been disclosed that embodiment be not limiting as the scope of the present invention.On the contrary, being contained in the modification of the spirit and scope of claims and impartial setting is included in the scope of the present invention.
Claims (10)
1. pre-melted type compound dephosphorization agent, it is characterised in that the pre-melted type compound dephosphorization agent is made up of by weight percentage following components and inevitable impurity：
Di-iron trioxide（Fe2O3）And ferrous oxide（FeO）Mixture 30% ~ 60%
Calcium oxide（CaO）
20%~50%
Alundum (Al2O3)（Al2O3）
0~10%
Silica（SiO2）
0~10%
Magnesia（MgO）
0~10%
Calcirm-fluoride（CaF2）
5%~30%。
2. pre-melted type compound dephosphorization agent according to claim 1, it is characterised in that the pre-melted type compound dephosphorization agent is made up of by weight percentage following components and inevitable impurity：
Di-iron trioxide（Fe2O3）And ferrous oxide（FeO）Mixture 40% ~ 50%
Calcium oxide（CaO）
30%~45%
Alundum (Al2O3)（Al2O3）
0~8%
Silica（SiO2）
0~8%
Magnesia（MgO）
0~8%
Calcirm-fluoride（CaF2）
5%~25%。
3. pre-melted type compound dephosphorization agent according to claim 2, it is characterised in that the pre-melted type compound dephosphorization agent is made up of by weight percentage following components and inevitable impurity：
Di-iron trioxide（Fe2O3）And ferrous oxide（FeO）Mixture 40%
Calcium oxide（CaO）
45%
Alundum (Al2O3)（Al2O3）
4%
Silica（SiO2）
3%
Magnesia（MgO）
2%
Calcirm-fluoride（CaF2）
6%。
4. pre-melted type compound dephosphorization agent according to claim 2, it is characterised in that the pre-melted type compound dephosphorization agent is made up of by weight percentage following components and inevitable impurity：
Di-iron trioxide（Fe2O3）And ferrous oxide（FeO）Mixture 45%
Calcium oxide（CaO）
40%
Alundum (Al2O3)（Al2O3）
2%
Silica（SiO2）
3%
Magnesia（MgO）
2%
Calcirm-fluoride（CaF2）
8%。
5. pre-melted type compound dephosphorization agent according to claim 2, it is characterised in that the pre-melted type compound dephosphorization agent is made up of by weight percentage following components and inevitable impurity：
Di-iron trioxide（Fe2O3）And ferrous oxide（FeO）Mixture 50%
Calcium oxide（CaO）
35%
Alundum (Al2O3)（Al2O3）
4%
Silica（SiO2） 3%
Magnesia（MgO）
2%
Calcirm-fluoride（CaF2）
6%。
6. pre-melted type compound dephosphorization agent according to claim 2, it is characterised in that the pre-melted type compound dephosphorization agent is made up of by weight percentage following components and inevitable impurity：
Di-iron trioxide（Fe2O3）And ferrous oxide（FeO）Mixture 55%
Calcium oxide（CaO）
25%
Alundum (Al2O3)（Al2O3）
4%
Silica（SiO2）
3%
Magnesia（MgO）
2%
Calcirm-fluoride（CaF2）
11%。
7. a kind of method of the pre-melted type compound dephosphorization agent prepared as described in any one in claim 1 to 6, it comprises the following steps：
（1）Above-mentioned component is crushed, is mixed and/or pelletizing,
（2）The fusing in 1100 DEG C ~ 1600 DEG C of temperature range by the product of gained；
（3）Jing after cooling, crushing, pre-melted type compound dephosphorization agent is obtained；
Wherein, resulting pre-melted type compound dephosphorization agent granularity is 1 ~ 30mm.
8. it is a kind of smelt ultra-low phosphoretic steel method, it is characterised in that：The method is mainly included the following steps that：
（1）Converter tapping：After converter smelting terminates, the end phosphorus content of converter is controlled below 0.02%, tapping temperature is controlled at 1560 DEG C ~ 1660 DEG C, deoxidation treatment is not carried out to molten steel in tapping process, and processed using pushing off the slag in tapping process；
（2）Converter tapping deep dephosphorization：Pre-melted type compound dephosphorization agent of the addition as described in any one in claim 1 to 6 in ladle is flowed to steel in converter tapping process, ladle is transported into Argon station after the completion of tapping, Argon stirring is carried out to molten steel；
（3）Skim：The slag on the molten steel surface after dephosphorization treatment is removed using Cinder Machine, is subsequently adding ladle covering agent；
（4）Deoxidation alloying refining treatment：Ladle is transported into refining station, deoxidation, alloying, temperature adjustment process is carried out；
（5）Continuous casting：Cast using whole process protection.
9. it is according to claim 8 it is a kind of smelt ultra-low phosphoretic steel method, it is characterised in that：
Wherein described pushing off the slag is processed to be realized using any one mode in floating plug, skimming ball, slag retaining cone or valve plate slag stopping；
Wherein described pre-melted type Dephosphorising agent is homogeneously added into ladle by tapping to tapping end, and with mixed with molten steel slag is washed into, and carries out deep dephosphorization.
10. according to a kind of method of the smelting ultra-low phosphoretic steel described in claim 8 or 9, it is characterised in that：Described pre-melted type compound dephosphorization agent consumption is 3 ~ 10 kgs/tonne of molten steel.
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- 2015-11-06 CN CN201510748095.XA patent/CN106676233A/en active Pending
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| CN112961962A (en) * | 2021-02-04 | 2021-06-15 | 东北大学 | Composite dephosphorizing agent for tapping after furnace, preparation method and application |
| CN113604735A (en) * | 2021-07-20 | 2021-11-05 | 山东钢铁股份有限公司 | Hot-rolled low-temperature-resistant H-shaped steel with yield strength of 420MPa and preparation method thereof |
| US20230121123A1 (en) * | 2021-10-19 | 2023-04-20 | University Of Science And Technology Beijing | Method of making steel by deeply dephosphorization in hot metal tank and decarburization using semi-steel with nearly zero phosphorus load in converter |
| US11674192B2 (en) * | 2021-10-19 | 2023-06-13 | University Of Science And Technology Beijing | Method of making steel by deeply dephosphorization in hot metal tank and decarburization using semi-steel with nearly zero phosphorus load in converter |
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