CN104232831A - Low-carbon ultra-low sulfur steel smelting method - Google Patents
Low-carbon ultra-low sulfur steel smelting method Download PDFInfo
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- CN104232831A CN104232831A CN201410444361.5A CN201410444361A CN104232831A CN 104232831 A CN104232831 A CN 104232831A CN 201410444361 A CN201410444361 A CN 201410444361A CN 104232831 A CN104232831 A CN 104232831A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/02—Dephosphorising or desulfurising
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/06—Deoxidising, e.g. killing
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/10—Handling in a vacuum
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C2300/00—Process aspects
- C21C2300/08—Particular sequence of the process steps
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Abstract
The invention discloses a low-carbon ultra-low sulfur steel smelting method. The method comprises the following technological processes: pouring molten iron into a tank, pretreatment of molten iron, oxygen remaining operation of a converter, RH furnace vacuum decarburization, alloying and vacuum degassing in an RH furnace, deoxidization of aluminium yarn/aluminium wire in an LF refining furnace, slagging by using lime and CCM. Through combination of molten iron desulphurization and drossing, optimization of a converter steel tapping and oxygen remaining system and a slagging system, the vacuum decarburization, alloying and degassing control in the RH furnace, and the aluminium wire diffusing deoxidation slagging and aluminium wire sediment deoxidation in the LF furnace, deep decarburization and desulphurization are carried out. With an emphasis on combination of convertor steel tapping and oxygen remaining operations, RH deep decarburization and LF furnace deep desulphurization, technical optimization is carried out; due to reasonable ladle argon bottom blowing control in the smelting process, carbon content control and metallurgical thermodynamics and dynamics conditions of desulphurization are given a full play; the RH furnace decarburization is stable; LF furnace slagging and desulphurization and recarburization control effects are obvious; and low-carbon ultra-low sulfur steel smelting is achieved.
Description
Technical field
The invention belongs to a kind of process for making of field of metallurgy, relate to the technique of smelting low carbon ultralow-sulfur steel carbon, sulphur content control.
Background technology
Sulphur can cause detrimentally affect to the performance of steel, and in steel, sulphur content is high, and the hot workability of steel can be made to degenerate, and namely causes " hot-short " property of steel.Along with the development of science and technology, society is also more and more higher to the requirement of ferrous materials, the particularly exploitation of hic resistance and anti-H2S corrosion steel, and in steel, sulphur content requires within 0.0010%, harsh sulphur content requirement, conventional smelting sulfur removal technology can not meet scale operation needs completely.While particularly part steel requires low-sulfur, in order to ensure yield behavior and welding property, carbon content need control in lower scope, but the dark desulfurization of LF stove, cause long electrode carburetting heat-up time serious, super low sulfur and low-carbon (LC) control to define contradiction.Therefore, develop a kind of low-carbon (LC) ultralow-sulfur steel smelting technology, become the development bottleneck of Ge Jia Iron And Steel Company research and development high added value variety steel and benefit growth point.In order to break through this restricted link, the present invention, based on theoretical calculation analysis, takes into full account the favourable condition of reaction between carbon and oxygen, through test in place repeatedly, successfully develops low-carbon (LC) ultralow-sulfur steel smelting technology.
Summary of the invention
The object of the present invention is to provide a kind of low-carbon (LC) ultralow-sulfur steel smelting process, effectively solve the contradiction that in smelting process, low-carbon (LC) and low-sulfur control, improve deoxidization desulfuration efficiency.
The technical scheme that the present invention realizes above goal of the invention is:
A kind of low-carbon (LC) ultralow-sulfur steel smelting process, it is characterized in that the method adopts molten iron ladle pouring → hot metal pretreatment → converter to stay oxygen operation → RH stove vacuum decarburization → RH stove alloying and vacuum outgas → LF refining furnace aluminium wire, aluminum steel deoxidation, lime slag making → CCM flow process, skimmed by desulfurizing iron, converter tapping stays the optimization of oxygen system and slagging regime, RH stove vacuum decarburization, alloying, degassed control, LF stove aluminium wire diffusive deoxidation slag making and feed aluminum steel bulk deoxidation and to combine dark desulfurization, the omnidistance reasonably ladle argon gas bottom blowing of smelting process controls, control the metallurgical thermodynamics and the dynamic conditions that give full play to carbon content control and desulfurization, realize [C]≤0.035% in molten steel, [S]≤0.0010%.
The present invention is by desulfurizing iron pre-treatment, converter tapping deoxidation system and slagging regime optimization, the dark decarburization of RH, alloying, degassed, the combination of the optimization of LF refining furnace deoxidation system and slagging regime, abundant decarburization, desulfurization, decrease heat-up time, effectively reduce electrode carburetting, efficiently solve the contradiction between low-carbon (LC), low-sulfur control.The present invention utilizes the Theoretical Calculation of alumina balanced reaction, in conjunction with actual deoxidation effectiveness, formulate accurate aluminium block add-on, converter tapping stays oxygen stable operation, ensures that RH arrives at a station oxygen level between 0.0300% ~ 0.0500%, the decarburization of RH stove by carbon content stability contorting within 0.010%, LF stove process deoxidation slag making is stablized, LF refining furnace finishing slag color whitens, and in slag, all iron content controls within 0.50%, reflects this slag and has stronger reductibility; After the process of LF stove terminates, in molten steel, sulphur content all can control 0.0010%, and carbon content all can control within 0.035%.Through test, adopt the inventive method, in molten steel, carbon, sulphur content control stable, and slab quality is good, and steel plate inspection qualification rate is stabilized in more than 99%, ensure that the production of the low-carbon (LC) ultralow-sulfur steel of high added value, meets the requirement of on-the-spot scale operation completely.
Accompanying drawing explanation
Fig. 1 is low-carbon (LC) ultralow-sulfur steel smelting process schema.
Fig. 2 is refining furnace terminal slag specimen design sketch.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
The invention discloses a kind of low-carbon (LC) ultralow-sulfur steel smelting process, adopt: oxygen operation → RH stove vacuum decarburization → RH stove alloying and vacuum outgas → LF refining furnace aluminium wire are stayed in molten iron ladle pouring → hot metal pretreatment → converter, aluminum steel deoxidation, lime slag making → CCM (continuous casting) technical process, skimmed by desulfurizing iron, converter tapping stays the optimization of oxygen system and slagging regime, RH stove vacuum decarburization, alloying, degassed control, LF stove aluminium wire diffusive deoxidation slag making and hello aluminum steel bulk deoxidation combine and carry out dark decarburization, desulfurization, emphasis stays oxygen to operate by converter tapping, the dark decarburization of RH and the dark desulfurization of LF stove combine and carry out process optimization, the omnidistance reasonably ladle argon gas bottom blowing of smelting process controls, give full play to metallurgical thermodynamics and the dynamic conditions of carbon content control and desulfurization, the decarburization of RH stove is stablized, LF stove slag making desulfurization and control carburetting successful, achieve [C]≤0.035% and [S]≤0.0010% in molten steel.
Low-carbon (LC) ultralow-sulfur steel smelting process flow process is as shown in Figure 1:
1, converter smelting process:
(1) hot metal pretreatment operation.Entering stove molten iron must skim clean through desulfurization pre-treatment, requires [S]≤0.005%, controls impurity (in steel scrap [S]≤0.010%) in steel scrap, reduce converter tapping sulphur content, alleviate the desulfurization burden that furnaceman's LF sequence makes strong reducing slag.
(2) pushing off the slag operation.The lower quantity of slag in strict control tapping process, controls the lower quantity of slag≤2kg/t, reduces the difficulty of converter tapping top slag deoxidation.
(3) temperature and carbon content control.Blow end point temperature is greater than 1680 DEG C, terminal [C]≤0.045%.
(3) tapping slag making.Tapping process adds composite refining slag and lime carries out ladle top slag upgrading, composite refining slag (composite refining slag ingredient: CaO55% ~ 65%, Al
2o
327% ~ 37%, SiO
2≤ 8.0%, H
2o≤0.5%, N≤0.05%) add-on ton steel is greater than 6Kg, and lime adding amount ton steel is greater than 3Kg.
(4) oxygen is stayed in tapping.Tapping does not add silicomanganese, and process adopts the weak deoxidation of aluminium block, adds aluminium block according to bessemerizing terminal oxygen level (sublance TSO value).After adding aluminium block, steel oxygen content in water need control at 300 ~ 500ppm.Shown in concrete add-on sees the following form.
Slag material and aluminium block joining day: tapping starts → and tapping adds slag material → tap for 30 seconds and adds aluminium block → tapping end to 1/3.
(5) steel ladle bottom argon blowing pneumatic control.Tapping process ladle bottom blowing gas flow is 200 ~ 300Nl/min, and tapping time controling is at 5-8min.
2, refining furnace smelting technology:
(1) RH vacuum decarburization process.After molten steel arrives RH stove process station, oxygen is determined in thermometric sampling, temperature is greater than 1590 DEG C and carries out vacuum decarburization (when temperature≤1590 DEG C, molten steel need return LF stove and be warmed up to more than 1620 DEG C and return the process of RH stove again), along with RH vacuum tightness reduces by normal atmosphere (An), molten steel decarburization (reaction between carbon and oxygen) starts, within vacuum tightness is reduced to 500Pa, reaction between carbon and oxygen terminates substantially (about 6 ~ 8min), add aluminum shot 200Kg/ stove and carry out deep deoxidation, continue vacuum and keep 2min, according to steel grades requirement, add silicomanganese (add-on by steel grades lower limit with addition of) alloy and carry out alloying.
(2) RH Fruit storage.Fruit storage is carried out after RH alloying, vacuum tightness is not more than 300Pa, and the hold-time is greater than 15min, RH vacuum decarburization, alloying, degassed whole process, ladle bottom blowing argon flow amount controls at 5 ~ 15Nl/min, and vacuum terminates molten steel handling and continues refining treatment to LF stove.
(3) LF stokehold phase operation.After molten steel to LF stove process station, adjustment ladle bottom blowing flow 300 ~ 400Nl/min.Add lime 3kg/ ton steel, aluminium wire 0.3kg/ ton steel, sampling analysis for after electrochemical slag 2 ~ 3min, lower electrode heats up.
(4) LF stove operation in mid-term (treatment time about 10min).According to LF stove first steel sample ingredient and slag condition thickness situation, add suitable lime and aluminium wire slag making desulfurization, lime adding amount ton steel is less than 2Kg, aluminium wire 0.2kg/ ton steel, sweetening process argon flow amount 350 ~ 500Nl/min, feed aluminum steel adjustment steel liquid aluminium content, feed aluminum steel and control argon flow amount 30 ~ 60Nl/min, aluminum steel feed quantity: remain on 0.05 ~ 0.06% scope to control aluminum steel feed quantity with aluminium content in smelting process molten steel, composition according to target steel grade carries out alloying, heat up 6 ~ 8min sampling analysis, and lower electrode continues intensification desulfurization.
(5) LF stove finishing operations (treatment time about 25min).According to LF stove second steel sample ingredient and slag condition thickness situation, add suitable lime and aluminium wire slag making desulfurization, lime adding amount ton steel is less than 2Kg, aluminium wire 0.2kg/ ton steel, sweetening process argon flow amount 350 ~ 500Nl/min, feed aluminum steel adjustment steel liquid aluminium content, feed aluminum steel and control argon flow amount 30 ~ 60Nl/min, aluminum steel feed quantity: remain on 0.03% ~ 0.05% scope to control aluminum steel feed quantity with aluminium content in smelting process molten steel, adds alloy and carries out alloying fine adjustment (guaranteeing that alloying constituent reaches steel grade target call); Lower electrode intensification desulfurization, sampling analysis.LF stove finishing operations flow process is repeated according to analytical results.
(6) Calcium treatment and soft stirring.After molten steel composition temperature is all qualified, in order to ensure that inclusion modification is removed, feed pure calcium line 180 ~ 200m/ stove (or calcium iron wire 350 ~ 400m/ stove) in molten steel, Calcium treatment terminates soft stirring and is greater than 12min, soft stirring Bottom Blowing Flow Rate Control: 10 ~ 60Nl/min.
Embodiment one
The present embodiment selects X65MS pipeline steel grade, smelts situation at 150 tons of converters, 150 tons of ladle furnaces.Its X65MS pipe line steel chemical composition is in table 1, and whole smelting process controls as follows:
Table 1 X65MS main chemical (%)
(1) bessemerize.Blow end point composition and temperature control in table 2.
Table 2 converter terminal composition (%)
(2) deoxidation slag making alloying after converter.Tapping process auxiliary material added order: start tapping → lime, refining slag → aluminium block, and after add-on and stove, Composition Control is in table 3.
Composition after table 3 stove
(3) RH process.RH is by reaction between carbon and oxygen decarburization, and add aluminium deep deoxidation, inclusion is removed in preliminary alloying and vacuum outgas.Concrete data in table 4, RH process closure component table 5.
Table 4 RH arrives at a station temperature and alloying situation
Table 5 RH closure component (%)
(4) refinement and deoxidation, slag making desulfurization, go to be mingled with technique.Arriving at a station of LF stove molten steel slag → control argon bottom-blowing 300 ~ 400Nl/min, heat temperature raising 3min → add lime, aluminium wire, hello aluminum steel → heating → lime, aluminium wire, hello aluminum steel → control argon bottom-blowing 350 ~ 500Nl/min → alloying → heating → alloy fine setting → heating → feed the aluminium → Calcium treatment → soft stirring of aluminum steel tune, concrete consumption is in table 6, refining treatment terminates slag specimen composition in table 7, slag specimen design sketch is shown in Fig. 1, and refining furnace terminal composition is in table 8.
Table 6 refining furnace feeds in raw material situation (kg)
Table 7 refining furnace terminates slag composition (%)
Table 8 refining furnace endpoint molten steel major ingredient (%)
(5) performance summary
This technique is by the Theoretical Calculation of alumina balanced reaction, in conjunction with on-the-spot actual deoxidation effectiveness, formulate accurate aluminium block add-on, oxygen stable operation is stayed in converter, ensures that RH arrives at a station oxygen level between 0.0300% ~ 0.0500%, and RH stove decarburization stability contorting is within 0.010%, LF stove process deoxidation slag making is stablized, LF refining furnace finishing slag color whitens, and in slag, all iron content controls within 0.50%, reflects this slag and has stronger reductibility; After the process of LF stove terminates, in molten steel, sulphur content all can control 0.0010%, and carbon content all can control within 0.030%, meets the requirement of on-the-spot scale operation.
Claims (10)
1. a low-carbon (LC) ultralow-sulfur steel smelting process, it is characterized in that the method adopts molten iron ladle pouring → hot metal pretreatment → converter to stay oxygen operation → RH stove vacuum decarburization → RH stove alloying and vacuum outgas → LF refining furnace aluminium wire, aluminum steel deoxidation, lime slag making → CCM flow process, skimmed by desulfurizing iron, converter tapping stays the optimization of oxygen system and slagging regime, the dark decarburization of RH stove vacuum, alloying, degassed control, LF stove aluminium wire diffusive deoxidation slag making and feed aluminum steel bulk deoxidation and to combine dark desulfurization, the omnidistance reasonably ladle argon gas bottom blowing of smelting process controls, give full play to metallurgical thermodynamics and the dynamic conditions of carbon content control and desulfurization, realize [C]≤0.035% in molten steel, [S]≤0.0010%.
2. low-carbon (LC) ultralow-sulfur steel smelting process according to claim 1, it is characterized in that: converter tapping stays oxygen, tapping process does not add silicomanganese, adopt the weak deoxidation of aluminium block, tap to 1/3 time according to bessemerizing terminal oxygen level and sublance TSO value adds aluminium block, after adding aluminium block, in molten steel, Control for Oxygen Content is at 300 ~ 500ppm, shown in concrete add-on sees the following form:
As TSO oxygen level >=1300ppm, often increase 100ppm oxygen and increase aluminium block 10Kg.
3. low-carbon (LC) ultralow-sulfur steel smelting process according to claim 1, it is characterized in that: RH stove vacuum decarburization, after molten steel arrives RH stove process station, oxygen is determined in thermometric sampling, temperature is greater than 1590 DEG C and carries out vacuum decarburization, when temperature≤1590 DEG C, molten steel returns LF stove and is warmed up to more than 1620 DEG C and returns the process of RH stove again, along with RH vacuum tightness reduces by normal atmosphere (An), molten steel decarburization starts, within vacuum tightness is reduced to 500Pa, reaction between carbon and oxygen terminates substantially, add aluminum shot 200Kg/ stove and carry out deep deoxidation, continue vacuum and keep 2min, the flow control of whole process argon bottom-blowing is at 5 ~ 15Nl/min.
4. low-carbon (LC) ultralow-sulfur steel smelting process according to claim 1, is characterized in that: after RH stove vacuum decarburization, according to steel grades requirement, adds silicomanganese and carry out alloying; Then carry out RH stove Fruit storage, vacuum tightness is not more than 300Pa, and the hold-time is greater than 15min, and the flow control of whole process argon bottom-blowing is at 5 ~ 15Nl/min.
5. low-carbon (LC) ultralow-sulfur steel smelting process according to claim 1, is characterized in that the dark desulfurization of LF stove:
Operation in early stage: after molten steel to LF stove process station, adjustment ladle bottom blowing flow 300 ~ 400Nl/min, for adding lime 3kg/ ton steel, aluminium wire 0.3kg/ ton steel after electrochemical slag 2 ~ 3min, sampling analysis, lower electrode heats up;
Mid-term operates: according to LF stove first steel sample ingredient and slag condition thickness situation, add suitable lime and aluminium wire slag making desulfurization, lime adding amount ton steel is less than 2 Kg, aluminium wire 0.2kg/ ton steel, sweetening process controls argon flow amount 350 ~ 500 Nl/min, feed aluminum steel adjustment steel liquid aluminium content, feed aluminum steel process control argon flow amount 30 ~ 60Nl/min, aluminum steel feed quantity: remain on 0.05 ~ 0.06% scope to control aluminum steel feed quantity with aluminium content in smelting process molten steel, composition according to target steel grade carries out alloying, heat up 6 ~ 8min sampling analysis, lower electrode continues intensification desulfurization,
Finishing operations: according to LF stove second steel sample ingredient and slag condition thickness situation, add suitable lime and aluminium wire slag making desulfurization, lime adding amount ton steel is less than 2 Kg, aluminium wire 0.2kg/ ton steel, sweetening process controls argon flow amount 350 ~ 500 Nl/min, feed aluminum steel adjustment steel liquid aluminium content, feed aluminum steel process control argon flow amount 30 ~ 60Nl/min, aluminum steel feed quantity: remain on 0.03% ~ 0.05% scope to control aluminum steel feed quantity with aluminium content in smelting process molten steel, adds alloy and carries out alloying fine adjustment and guarantee that alloying constituent reaches steel grade target call; Lower electrode continues intensification desulfurization, sampling analysis, repeats finishing operations flow process until meet component requirements.
6. according to the arbitrary described low-carbon (LC) ultralow-sulfur steel smelting process of claim 1-5, it is characterized in that: enter stove molten iron and skim clean through desulfurization pre-treatment, require [S]≤0.005%, control impurity in steel scrap, reduce converter tapping sulphur content, alleviate LF operation and make the desulfurization of strong reducing slag and the burden of carburetting.
7. according to the arbitrary described low-carbon (LC) ultralow-sulfur steel smelting process of claim 1-5, it is characterized in that: the strict lower quantity of slag≤2kg/t controlled in tapping process, prevents ladle top slag peroxidation.
8. according to the arbitrary described low-carbon (LC) ultralow-sulfur steel smelting process of claim 1-5, it is characterized in that: control blow end point temperature and be greater than 1680 DEG C, terminal [C]≤0.045%, tap and add composite refining slag after 30 seconds and lime carries out ladle top slag upgrading, composite refining slag add-on ton steel is greater than 6Kg, lime adding amount ton steel is greater than 3Kg, and the component of composite refining slag and weight percent thereof are: CaO 55% ~ 65%, Al
2o
327% ~ 37%, SiO
2≤ 8.0%, H
2o≤0.5%, N≤0.05%.
9. according to the arbitrary described low-carbon (LC) ultralow-sulfur steel smelting process of claim 1-5, it is characterized in that: tapping process ladle bottom blowing gas flow is 200 ~ 300Nl/min, tapping time controling is at 5-8min.
10. according to the arbitrary described low-carbon (LC) ultralow-sulfur steel smelting process of claim 1-5, it is characterized in that: after molten steel composition temperature is all qualified, in order to ensure that inclusion modification is removed, pure calcium line 180 ~ 200m/ stove is fed or calcium iron wire 350 ~ 400m/ stove carries out calcification processing in molten steel, Calcium treatment terminates soft stirring and is greater than 12min, and the flow control of soft whipping process argon bottom-blowing is at 10 ~ 60 Nl/min.
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