CN106609313A - High-purity rare earth steel treatment method - Google Patents

High-purity rare earth steel treatment method Download PDF

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Publication number
CN106609313A
CN106609313A CN201710059980.6A CN201710059980A CN106609313A CN 106609313 A CN106609313 A CN 106609313A CN 201710059980 A CN201710059980 A CN 201710059980A CN 106609313 A CN106609313 A CN 106609313A
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rare earth
refining
steel
vacuum
purity
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CN106609313B (en
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刘宏伟
栾义坤
傅排先
胡小强
李殿中
李依依
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Zhongke Xiwang Special Steel Co ltd
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Institute of Metal Research of CAS
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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
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/52—Manufacture of steel in electric furnaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/28—Manufacture of steel in the converter
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0006—Adding metallic additives
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/10—Handling in a vacuum
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Treatment Of Steel In Its Molten State (AREA)

Abstract

The invention relates to the field of molten water purifying treatment and particularly relates to a high-purity rare earth steel treatment method. The method is applied to a preparation blank of a process I: electric furnace/converter; LF refining; VD/RH vacuum treatment; soft blowing; continuous casting/die casting; or a process II: converter; RH vacuum treatment; soft blowing; continuous casting. The method specifically comprises the step of adding lanthanum and cerium mixed pure rare earth into three molten steel refining treatment: LF refining, VD/RH vacuum treatment or soft blowing, wherein the adding amount is dependent on the total content of dissolved oxygen O dissolved oxygen, total oxygen T.O and sulfur content S in the molten steel and alkalinity of refining slag R=CaO/SiO2, FeO+MnO, thereby achieving action effects of purifying the molten steel by rare earth and deteriorating fine occluded foreign substances. The method combines a refining operation process to reasonably add rare earth according to composition of sulfur, oxygen content and refined slag in the molten steel and highlights the action effects of purifying the molten steel and deteriorating fine occluded foreign substances by virtue of rare earth, so that the degree of purity of the molten steel is enhanced, and the occluded foreign substances are refined.

Description

A kind of high-purity rare earth steel processing method
Technical field
The present invention relates to molten steel sublimate process field, specially a kind of high-purity rare earth steel processing method.
Background technology
Molten Steel Cleanliness control be high-quality steel for middle most essential steps, and inclusion content and inclusion size are in steel The most important index of degree of purity.Currently, the blank of steel is mainly adopted：Technique 1. (electric furnace/converter → LF refining → VD/RH vacuum Process → soft blow → continuous casting/molding) or technique 2. (converter → RH application of vacuum → soft blow → continuous casting) preparation.But due to production stream Journey is long, and controlling unit is more, the higher problem with the larger field trash of size of long-term existence inclusion content of steel, steel usually occurs Situation of the middle total oxygen content more than 15ppm, and field trash grade is also higher.Accordingly, it would be desirable to a kind of effective, stable molten steel Purification method improves the degree of purity of steel.It is a kind of preferable high and rare earth has deep deoxidation, the action effect of modifying-refining field trash Clean steel processing method.
The content of the invention
It is an object of the invention to provide a kind of high-purity rare earth steel processing method, solve technique of the prior art 1. or Entire oxygen content in the steel content is more than 15ppm when 2. technique prepare steel billet, and field trash grade also compares a high-tech difficult problem.According to enforcement Technique refining process steel oxygen in water (ODissolved oxygen), total oxygen (T.O), sulfur content and refining slag ingredient, carry out reasonable rare earth and contain Amount addition, realizes molten steel deep deoxidation, modifying-refining field trash action effect.
The technical scheme is that：
A kind of high-purity rare earth steel processing method, the method is " technique is 1.：Electric furnace/converter → LF refining → VD/RH vacuum Process → soft blow → continuous casting/molding " or " technique is 2.：Preparing for converter → RH application of vacuum → soft blow → continuous casting " should in blank With, specifically lanthanum cerium mixing pure rare earth is added in LF refining, three liquid steel refinings of VD/RH applications of vacuum or soft blow are processed, add Amount is then according to steel oxygen in water ODissolved oxygen, total oxygen T.O, sulfur content S and refining basicity of slag R=CaO/SiO2, FeO+MnO always contains Amount is added, and reaches rare earth purification molten steel, the action effect of rotten fine foreign matter.
Described high-purity rare earth steel processing method, the method during 1. technique prepare blank using when, LF refining, VD/RH applications of vacuum, three liquid steel refinings of soft blow add lanthanum cerium mixing pure rare earth in processing；Wherein, plus the angle of incidence is in LF white slags After formation, after FeO+MnO total contents are less than 1.0%.
Described high-purity rare earth steel processing method, when in LF refining station 20ppm≤T.O≤30ppm, 0.0030wt% ≤ S≤0.0050wt%, 5ppm≤ODissolved oxygen≤ 10ppm, during refining basicity of slag R >=2.5, rare earth is in LF refining station addition 0.05wt%～0.030%, rare earth is 0.03wt%～0.02wt% in VD/RH application of vacuum stations addition, and rare earth is soft Station addition is blown for 0.02wt%～0.01wt%；As LF refining station T.O≤20ppm, S≤0.0030wt%, ODissolved oxygen≤ 5ppm, during refining basicity of slag R >=2.5, rare earth is 0.03wt%～0.025wt% in LF refining station addition, and rare earth is in VD/ RH application of vacuum station addition be 0.025wt%～0.02%, rare earth soft blow station addition be 0.02wt%～ 0.01wt%.
Described high-purity rare earth steel processing method, when applying during 2. technique prepare blank, converter molten iron is needed the method Desulfurization operations are carried out, then S≤0.0050wt% carries out RH application of vacuum operation；Need to carry out deoxidation behaviour after RH application of vacuum Make, ODissolved oxygenRare earth is added after≤10ppm, it is desirable to which FeO+MnO total contents are less than 5.0%, add rare earth, rare earth to add after deoxidation operation Enter amount for 0.015wt%～0.025wt%.
Described high-purity rare earth steel processing method, in mixed rare earth of lanthanum and cerium, part by weight shared by lanthanum more than 15%, More than 50%, the total oxygen content in rare earth is in below 200ppm for part by weight shared by cerium.
Described high-purity rare earth steel processing method, in continuous casting/molding station, will prevent secondary oxidation, its Main Means It is：At steel contacts, including tundish, long nozzle are mainly using resistant to corrosion preferably magnesia and zirconia refractory, and Tundish and long nozzle, ladle nozzle and feed trumpet junction, using closed argon gas-sealed.
Described high-purity rare earth steel processing method, the method reaches rare earth purification molten steel, the work of rotten fine foreign matter With effect, refer to by RE-treated and rationally addition, the T.O≤15ppm in final steel, Jing RE Modifieds size≤5 μm Quantitative proportion is more than 85% shared by spherical oxysulfide.
Advantages of the present invention and beneficial effect are：
1st, the present invention can be in technique 1. (electric furnace/converter → LF refining → VD/RH applications of vacuum → soft blow → continuous casting/molding) Or technique 2. (converter → RH application of vacuum → soft blow → continuous casting) is prepared in blank and applied, overcome rare earth block mouth of a river problem.
2nd, the present invention has lifting Molten Steel Cleanliness action effect, becomes can the T.O≤15ppm in final steel, Jing rare earths Spherical oxysulfide (size≤5 μm) proportion of matter more than 85%, the high problem of effectively solving steel inclusion grade.
Specific embodiment
In specific implementation process, high-purity rare earth steel processing method of the present invention, the method can technique 1. (electric furnace/turn Stove → LF refining → VD/RH applications of vacuum → soft blow → continuous casting/molding) or technique 2. (converter → RH application of vacuum → soft blow → Continuous casting) prepare in blank and apply, specifically can add in LF refining, three liquid steel refinings of VD/RH applications of vacuum or soft blow are processed Enter.The rare earth of addition is lanthanum cerium mixing pure rare earth, and addition is then according to steel oxygen in water (ODissolved oxygen), total oxygen (T.O), sulfur content (S) and refining basicity of slag (R=CaO/SiO2), FeO+MnO total contents be added, reach rare earth purification molten steel, rotten thin The action effect of little field trash.Additionally, in continuous casting/molding station, to prevent secondary oxidation.
The method, specifically can be in LF refining, VD/RH applications of vacuum, soft blow three when applying during 1. technique prepare blank Add in liquid steel refining process.Wherein, plus the angle of incidence should after LF white slags are formed, FeO+MnO total contents less than 1.0wt% it Afterwards.Addition is also contemplated that dissolved oxygen (ODissolved oxygen), total oxygen (T.O), sulfur content and refining basicity of slag (R=CaO/SiO2).Plus Enter amount it is also contemplated that dissolved oxygen (ODissolved oxygen), total oxygen (T.O), sulfur content and refining basicity of slag (R=CaO/SiO2).Specially： When in LF refining station 20ppm≤T.O≤30ppm, 0.0030wt%≤S≤0.0050wt%, 5ppm≤ODissolved oxygen≤ 10ppm, During refining basicity of slag R >=2.5, rare earth exists in 0.05wt%～0.030wt% that LF refining station addition is molten steel amount, rare earth VD/RH application of vacuum stations addition is the 0.03wt%～0.02wt% of molten steel amount, and rare earth is steel in soft blow station addition 0.02wt%～the 0.01wt% of the water yield；As LF refining station T.O≤20ppm, S≤0.0030wt%, ODissolved oxygen≤ 5ppm, refining During basicity of slag R >=2.5, in 0.03wt%～0.025wt% that LF refining station addition is molten steel amount, rare earth is in VD/ for rare earth RH application of vacuum station addition is the 0.025wt%～0.02wt% of molten steel amount, and rare earth is molten steel in soft blow station addition 0.02wt%～the 0.01wt% of amount.
Technique 2. in, converter molten iron need to carry out desulfurization operations, and then S≤0.0050wt% carries out RH application of vacuum behaviour Make.Need to carry out deoxidation operation, O after RH application of vacuumDissolved oxygenRare earth is added after≤10ppm, it is desirable to which FeO+MnO total contents are less than 5.0wt%, adds rare earth after deoxidation operation, rare earth adding quantity is the 0.015wt%～0.025wt% of molten steel amount.
The rare earth that the method is added is mixed rare earth of lanthanum and cerium, and lanthanum proportion should be in more than 15wt% in mischmetal (preferably 30wt%), cerium proportion should be at more than 50wt% (preferably 70wt%), and the total oxygen content in rare earth exists Below 200ppm (being preferably 80ppm).
The method is described in continuous casting/molding station, to prevent secondary oxidation.At its Main Means, with steel contacts, including Tundish, long nozzle mainly adopt resistant to corrosion preferably magnesia and zirconia refractory, and in tundish and long nozzle, ladle water Mouth and feed trumpet junction, using closed argon gas-sealed.
The method reaches rare earth purification molten steel, the action effect of rotten fine foreign matter, refers to by RE-treated and conjunction Reason addition, the T.O≤15ppm in final steel, quantitative proportion shared by the spherical oxysulfide (size≤5 μm) of Jing RE Modifieds surpasses Cross 85%.
The present invention is described in further detail below by embodiment.
Embodiment 1
In the present embodiment, Q345E using technique 1., concrete technology be converter → LF refining → RH application of vacuum → soft blow → Continuous casting, molten steel amount is 180 tons.After LF white slags are formed, FeO+MnO total contents=0.8wt%, T.O=in LF refining station 25ppm, S=0.0042wt%, ODissolved oxygen=8ppm, during refining basicity of slag R=3.2, enters respectively in LF, RH, soft blow addition rare earth The stove Q345E of row 3 is produced.Wherein, rare earth is being 0.045wt% in LF refining station addition, and rare earth is in RH station additions 0.025wt%, rare earth is 0.018wt% in soft blow station addition, as a result such as following table：
Effect after the continuous casting steel RE-treated of table 1
Heat (batch) number Rare earth addition Finished product total oxygen content ppm Spherical impurities quantitative proportion
1-1 ﹟ LF:0.045wt% 14 85%
1-2 ﹟ RH:0.025wt% 12 87%
1-3 ﹟ Soft blow:0.018wt% 10 87%
Embodiment 2
In the present embodiment, Q345E using technique 1., concrete technology be converter → LF refining → RH application of vacuum → soft blow → Continuous casting, molten steel amount is 180 tons.After LF white slags are formed, FeO+MnO total contents=0.6wt%, T.O=in LF refining station 15ppm, S=0.0025wt%, ODissolved oxygen=5ppm, during refining basicity of slag R=4.5, enters respectively in LF, RH, soft blow addition rare earth The stove Q345E of row 3 is produced.Wherein, rare earth is 0.028wt% in LF refining station addition, and rare earth is in RH station additions 0.022wt%, rare earth is 0.015wt% in soft blow station addition, as a result such as following table：
Effect after the continuous casting steel RE-treated of table 2
Heat (batch) number Rare earth addition Finished product total oxygen content ppm Spherical impurities quantitative proportion
2-1 ﹟ LF:0.028wt% 12 86%
2-2 ﹟ RH:0.022wt% 11 88%
2-3 ﹟ Soft blow:0.015wt% 10 90%
Embodiment 3
In the present embodiment, using technique 1., concrete technology is electric furnace → LF refining → VD applications of vacuum → soft blow to 42CrMo → molding, molten steel amount is 80 tons.After LF white slags are formed, FeO+MnO total contents=0.5wt%, T.O=in LF refining station 12ppm, S=0.0018wt%, ODissolved oxygen=4ppm, during refining basicity of slag R=5.3, enters respectively in LF, RH, soft blow addition rare earth The stove 42CrMo of row 3 is produced.Wherein, rare earth is 0.030wt% in LF refining station addition, and rare earth adds in VD application of vacuum stations It is 0.020wt% to enter amount, and rare earth is 0.015wt% in soft blow station addition, as a result such as following table：
Effect after the molding molten steel RE-treated of table 3
Heat (batch) number Rare earth addition Finished product total oxygen content ppm Spherical impurities quantitative proportion
3-1 ﹟ LF:0.030wt% 11 87%
3-2 ﹟ VD:0.020wt% 10 90%
3-3 ﹟ Soft blow:0.015wt% 9 90%
Embodiment 4
In the present embodiment, using technique 2., concrete technology is converter → RH application of vacuum → soft blow → company to low-carbon (LC) automobile steel Casting.Before RE-treated, converter molten iron need to carry out desulfurization operations, and then S=0.0036wt% carries out RH application of vacuum operation. Need to carry out deoxidation operation, O after RH application of vacuumDissolved oxygenRare earth is added after=8ppm, it is desirable to FeO+MnO total contents=3.5wt%, taken off Rare earth is added after oxygen operation, rare earth adding quantity is 0.020wt%, as a result such as following table：
Embodiment result shows that the inventive method is grasped according to sulphur, oxygen content and refining slag composition in molten steel with reference to refining Make technique, carry out the action effects such as reasonable rare earth addition, prominent RE Elements on Steel Water warfare, inclusion modification, make Molten Steel Cleanliness Lifted, and refine field trash.The method process makes complete in steel with disperse spherical rare-earth type impurity effect is sufficiently formed , in below 15ppm, spherical impurities of the size below 5 μm are more than 85% for oxygen content (T.O).

Claims (7)

1. a kind of high-purity rare earth steel processing method, it is characterised in that the method is " technique is 1.：Electric furnace/converter → LF refining → VD/RH applications of vacuum → soft blow → continuous casting/molding " or " technique is 2.：The preparation of converter → RH application of vacuum → soft blow → continuous casting " Apply in blank, specifically add the mixing of lanthanum cerium pure dilute in LF refining, three liquid steel refinings of VD/RH applications of vacuum or soft blow are processed Soil, addition is then according to steel oxygen in water ODissolved oxygen, total oxygen T.O, sulfur content S and refining basicity of slag R=CaO/SiO2、FeO+ MnO total contents are added, and reach rare earth purification molten steel, the action effect of rotten fine foreign matter.
2. high-purity rare earth steel processing method according to claim 1, it is characterised in that 1. the method prepares base in technique When applying in material, in LF refining, VD/RH applications of vacuum, three liquid steel refinings of soft blow are processed lanthanum cerium mixing pure rare earth is added；Its In, plus the angle of incidence is after LF white slags are formed, after FeO+MnO total contents are less than 1.0%.
3. high-purity rare earth steel processing method according to claim 1 and 2, it is characterised in that when in LF refining station 20ppm≤T.O≤30ppm, 0.0030wt%≤S≤0.0050wt%, 5ppm≤ODissolved oxygen≤ 10ppm, refining basicity of slag R >= When 2.5, rare earth is 0.05wt%～0.030% in LF refining station addition, and rare earth is in VD/RH application of vacuum station additions For 0.03wt%～0.02wt%, rare earth is 0.02wt%～0.01wt% in soft blow station addition；As LF refining station T.O ≤ 20ppm, S≤0.0030wt%, ODissolved oxygen≤ 5ppm, during refining basicity of slag R >=2.5, rare earth is in LF refining station addition 0.03wt%～0.025wt%, rare earth is 0.025wt%～0.02% in VD/RH application of vacuum stations addition, and rare earth is soft Station addition is blown for 0.02wt%～0.01wt%.
4. high-purity rare earth steel processing method according to claim 1, it is characterised in that 2. the method prepares base in technique When applying in material, converter molten iron need to carry out desulfurization operations, and then S≤0.0050wt% carries out RH application of vacuum operation；It is true in RH Need to carry out deoxidation operation, O after the reason of vacancyDissolved oxygenRare earth is added after≤10ppm, it is desirable to which FeO+MnO total contents are less than 5.0%, deoxidation Rare earth is added after operation, rare earth adding quantity is 0.015wt%～0.025wt%.
5. high-purity rare earth steel processing method according to claim 1, it is characterised in that in mixed rare earth of lanthanum and cerium, lanthanum More than 15%, more than 50%, the total oxygen content in rare earth is in below 200ppm for part by weight shared by cerium for shared part by weight.
6. high-purity rare earth steel processing method according to claim 1, it is characterised in that in continuous casting/molding station, to prevent Only secondary oxidation, its Main Means is：At steel contacts, including tundish, long nozzle mainly adopt the preferable magnesium of resistant to corrosion Matter and zirconia refractory, and in tundish and long nozzle, ladle nozzle and feed trumpet junction, it is close using closed argon gas Envelope.
7. high-purity rare earth steel processing method according to claim 1, it is characterised in that the method reaches rare earth purification steel The action effect of water, rotten fine foreign matter, refers to by RE-treated and rationally addition, the T.O≤15ppm in final steel, Quantitative proportion is more than 85% shared by the spherical oxysulfide of Jing RE Modifieds size≤5 μm.
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CN109680215A (en) * 2019-03-06 2019-04-26 中国科学院金属研究所 A kind of refractory steel and preparation method thereof
CN110453036A (en) * 2019-09-09 2019-11-15 中国科学院金属研究所 A method of rotary wheel of water turbine is improved by rare earth treatment and resists dotted Cavitation
CN110484811A (en) * 2019-09-10 2019-11-22 中国科学院金属研究所 A kind of ultra-clean rare earth steel and inclusion conditioning control method
CN110527781A (en) * 2019-08-06 2019-12-03 武汉恒威宸装备制造有限公司 A kind of cinder ladle raw material processing method suitable for Copper making working condition
CN110564914A (en) * 2018-06-06 2019-12-13 中国科学院金属研究所 Method for improving low-temperature impact toughness of low-alloy bainite steel by rare earth microalloying
CN110629118A (en) * 2019-10-29 2019-12-31 成都先进金属材料产业技术研究院有限公司 Medium-low carbon industrial ultra-pure iron and production method thereof
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