CN107868900B - A kind of ultralow phosphorus faces the production method of hydrogen steel - Google Patents

A kind of ultralow phosphorus faces the production method of hydrogen steel Download PDF

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CN107868900B
CN107868900B CN201711158046.6A CN201711158046A CN107868900B CN 107868900 B CN107868900 B CN 107868900B CN 201711158046 A CN201711158046 A CN 201711158046A CN 107868900 B CN107868900 B CN 107868900B
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steel
molten steel
refining
molten
slag
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CN107868900A (en
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朱书成
刘丹
许少普
赵迪
郭艳芳
黄红乾
李红阳
高照海
康文举
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Nanyang Hanye Special Steel Co Ltd
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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
    • C22C33/04—Making ferrous alloys by melting
    • 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
    • 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
    • C21C7/0087—Treatment of slags covering the steel bath, e.g. for separating slag from the molten metal
    • 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
    • C21C7/068—Decarburising
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Treatment Of Steel In Its Molten State (AREA)

Abstract

The present invention provides the production methods that a kind of ultralow phosphorus faces hydrogen steel, it is related to metal material technical field of smelting, it successively includes molten iron pretreatment, LD converter is smelted, LF refining, take off Slag treatment, secondary LF refining, VD is vacuum-treated and continuous casting, specifically, molten iron pretreatment is carried out using KR method, LD converter smelts link and peroxidating is taken to tap, it keeps under strict control end phosphorus content, one time slag material is added in LF refining link, carry out initial refining dephosphorization, molten steel phosphorus content is set to reach 0.002 ~ 0.003%, it skims after qualification, secondary LF refining is substantially carried out composition adjustment and degree of purity improves, VD vacuum processing is de-gassed, slab is obtained through continuous casting.Relevant criterion requirement, steel plate chemical composition stability are fully met using HIC the and SSCC performance that ultralow phosphorus faces hydrogen steel obtained by this production method；Harmful chemical component p and s content is low；Non-metallic inclusion control is good；Slab quality is good.

Description

A kind of ultralow phosphorus faces the production method of hydrogen steel
Technical field
The present invention relates to metal material technical field of smelting, and in particular to a kind of ultralow phosphorus faces the production method of hydrogen steel.
Background technique
Phosphorus is that steel-making link needs one of harmful element of priority control, and phosphorus mainly influences the low temperature impact properties of steel, The high steel of phosphorus content are also easy to produce " cold short " at low temperatures.With the continuous development of science and technology, present steel industry pair The various performance requirements of steel are higher and higher, and especially in terms of facing hydrogen tank steel, such steel are to reach certain performance, finished product Phosphorus requires below 0.008% more.Under regular situation, there are two types of the dephosphorizations of making steel link, first is that molten iron takes blowing process dephosphorization, One is converter links to smelt dephosphorization.The former is affected to steel-making cost, does not use generally at present；The latter's smelting process turns Furnace dephosphorization rate can achieve 90% or more, but be constrained to steel-making cost, chemical reaction equilibrium and the protection to converter lining, The phosphorus content of such method smelting endpoint is still difficult to reach the requirement for facing hydrogen tank steel.
The patent of Publication No. CN103540833A discloses converter smelting and the external refining of a kind of hic resistance/SSCC steel Control method.Using the station converter-CAS-LF refining-VD/RH vacuum-Calcium treatment-soft blow-continuous casting smelting process route.Pass through To converter steelmaking process technology controlling and process, obtain meeting the low-phosphorous requirement of hic resistance/SSCC steel, meanwhile, by converter tapping mistake The strong deoxidation of Cheng Jinhang, alloying and wash heat are sloughed in molten steel with removing part deoxidation type inclusion using being sufficiently stirred for wash heat 60% or more sulphur.During LF refining, by adjusting the ingredient of refinery cinder, high alkalinity, high Al are obtained2O3, strong reducing property Refinery cinder so that field trash is realized transformation and removal to low melting point by the balance between clinker-molten steel-field trash.? It is vacuum-treated furnace and keeps suitable vacuum processing time and vacuum degree, to remove portion gas and field trash, break in empty backward molten steel Excessive calcium line is fed, soft blow then is carried out to molten steel and stirs 20min or more, obtains Ultra Low-oxygen and super-low sulfur molten steel.The invention Although hic resistance/SSCC steel obtained by production method meets HIC and SSCC test stone, but inclusion behavior and content, Yi Jihan Phosphorus amount is still higher, is further improved.
Steel enterprise Handan, Hebei iron company (Lu Qiaoting, Feng Liguo, Jia Gaifeng hydrogen sulfide corrosion resistant container steel Q345R (R-HIC) production practices [J] China metallurgy, 2014 (9): 29-32) at the beginning of 2013, start to be dedicated to hydrogen sulfide corrosion resistant The exploitation of pressure vessel steel Q345R (R-HIC), by the content for taking harmful chemicals element p and s in strict control steel；Subtract Few nonmetallic inclusionsin steel content；Maintenance continuous casting machine meticulously, guarantees the measures such as Inner Quality of Billet, successfully produces Hydrogen sulfide corrosion resistant steel plate of pressure vessel Q345R (R-HIC).The process route of hydrogen sulfide corrosion resistant container panel are as follows: desulphurised hot metal → top bottom blowing → LF refining → RH refining → sheet billet continuous casting → cutting → finishing → heating of plate blank → high-pressure water descaling → Rolling → roller repairing → thermal straightening → cold bed cooling → upper and lower surface inspection → shearing → steel plate mark → qualified product storage.It is logical Crossing P content in the chemical component of steel plate obtained by above-mentioned technique is 0.0102%, when which thinks P content > 0.012%, phosphorus it is inclined Analysis can sharply increase, and segregated zone hardness is promoted to increase, and in line of segragation, its hardenability is about 2 times of carbon, this makes under Properties of HIC resistance Drop.
The patent of Publication No. CN102766729A provides a kind of low-phosphorous control method of high speed axles steel, it includes It is following successively the step of: I molten iron pretreatment will contain P≤0.105%, the molten iron of S≤0.050% is pre-processed；II electric furnace smelting Steel scrap and pretreated molten iron are added electric furnace smelting, pretreated weight of molten iron ratio >=70%, P in steel scrap furnace charge≤ 0.035%, molten bath dephosphorization temperature is 1560 ~ 1580 DEG C, the whole progress foam slag operation after molten bath is formed, electric furnace steel tapping [C] >= 0.08%, [P]≤0.004%；Tapping Shi Liugang, slag is stayed；III LF refining technique LF refining whole process argon bottom-blowing；Using high Al2O3Contain The high alkalinity R(CaO/SiO of amount2The slag system of)=4.0 ~ 6.0 carries out slag making, deoxidation；IV VD processing technique vacuum degree≤67Pa is kept Time 25 minutes or more, sky is broken, immediately plus coverture.The steel that the low-phosphorous control method of the axle steel for high-speed motor car is produced is applicable in In axle steel for high-speed motor car, [P]≤6 × 10 can be made in steel-6, non-metallic inclusion A class, B class, C class, D type impurity grade Not no more than 0.5 grade.But the targeted steel grade of the low-phosphorous control method of the invention is mainly the EA4T(Germany trade mark) steel, by it Disclosure is it is found that the steel grade and Q345R steel grade, 15GrMoR steel grades difference are obvious, influence factor suffered by low-phosphorous control There can be difference, therefore be not particularly suited for facing the ultralow phosphorus control of hydrogen steel Q345R and 15GrMoR, low-phosphorous control in actual production Effect is undesirable.
The patent of Publication No. CN102367503A provides a kind of method for controlling phosphorus, sulphur and hydrogen content in molten steel, includes Following steps: molten iron pretreatment desulfurizing is carried out using KR；Molten iron after desulfurization is put into dephosphorization converter and carries out dephosphorization treatment；It will take off Molten iron after phosphorus is put into decarburization converter and is smelted；Decarburization converter tapping simultaneously carries out adding ferro-aluminum deoxidation and slag charge adjusting is added to determine slag alkali The operation of degree；RH refining.The invention uses low sulfur content, easy melting waste steel by molten iron pretreatment desulfurizing, dephosphorization, guarantees Converter terminal P≤60ppm, S≤100ppm；Converter tapping process is added the additional amount of aluminum amount and slag charge by control, opportunity is added, Realize wash heat desulfurization effect, guarantee refines into the station RH P≤80ppm, S≤60ppm and realizes smelting after handling degassing refining by RH Refine the purpose of low-phosphorous, low-sulfur, low hydrogen steel.But practice have shown that the invention is controlled to the side of phosphorus, sulphur and hydrogen content in molten steel Method is used to face the ultralow phosphorus control of hydrogen steel Q345R and 15GrMoR, the control requirement of ultralow phosphorus is not achieved, HIC and SSCC performance is not It meets the requirements of the standard.
With the development of technology, face hydrogen tank steel at present higher performance is proposed to Q345R and 15GrMoR steel grade and want It asks, known phosphorus is quite big on the influence of the performance of finished steel, therefore face hydrogen the steel Q345R and 15GrMoR that obtain more low phosphorus content are Improve the necessary ways of its service performance.
Summary of the invention
In view of this, having technical problem to be solved by the invention is to provide the production method that a kind of ultralow phosphorus faces hydrogen steel The phosphorus content that hydrogen steel especially faces in hydrogen steel Q345R and 15GrMoR is faced in effect control, improves the comprehensive performance for facing hydrogen steel.
In order to solve the above technical problems, the technical scheme adopted by the invention is that:
A kind of ultralow phosphorus faces the production method of hydrogen steel, comprising the following steps:
Step S1: molten iron pretreatment, molten iron is after KR method desulfurization process, temperature >=1350 DEG C, sulfur content≤0.010%；
Step S2:LD converter smelting, converter smelting endpoint, carbon content 0.02% ~ 0.04% in molten steel, phosphorus content≤ 0.012%, not killing, slag material and alloy during this, and without gon technics, tapping finishes, and molten steel is in converter Argon station afterwards carries out thermometric；
A slag material is added in S3: LF refining of step, this process, control the carbon content of the slag material≤ 1.0%, silicone content≤1.0%, adjustment electric current to maximum value is rapidly heated, when liquid steel temperature rises to 1585 DEG C, lifts electrode, Argon flow is adjusted to 1000NL/min, strong Argon 5min, sampling analysis, and molten steel phosphorus content 0.002 ~ 0.003% reaches primary LF refining dephosphorization controlling value；
Step S4: taking off Slag treatment, and molten steel is hung to station of skimming and is skimmed, and controls the oxidisability quantity of slag on liquid steel level ≤ 4.0kg/t molten steel；
Step S5: secondary LF refining, molten steel are hung to LF furnace again and carry out double refining, to adjust molten steel composition and removal folder Sundries；
Step S6:VD is vacuum-treated, Maxwell vacuscope measurement of vacuum≤67Pa, and the dwell time 18 minutes, pressure maintaining period Continue Argon, makes the naked eye diameter in molten steel face in 600mm or more；
Step S7: continuous casting, the middle packet degree of superheat≤25 DEG C, pulling rate 0.85m/min.
Preferably, the temperature of molten iron is 1360 ~ 1370 DEG C in the molten iron pretreatment.
Preferably, in the LD converter smelting process, the rifle position that blows early period control is in 1.3m, middle and later periods blowing rifle position control Between 0.9-1.1m, one fall temperature be 1550 DEG C, point blow the time control within 2min, point blow number≤2 time.
Preferably, in the LD converter smelting process, oxygen content >=1000ppm is controlled.
Preferably, a slag material is lime, iron scale and Fluorite pellet, and the lime adding amount is 7 ~ 8kg/t Molten steel, the iron scale additional amount are 4 ~ 5kg/t molten steel, and the Fluorite pellet additional amount is 2 ~ 3.5kg/t molten steel.
Preferably, CaO90wt%, SiO are contained in the lime23wt%, the activity degree of the lime are 300 ~ 350ml；It is described TFe content is in 86wt% or more in iron scale；Contain CaF82wt%, SiO in the Fluorite pellet21.3wt%。
Preferably, the secondary LF refining specifically sequentially includes the following steps:
A, the molten steel for being hung to LF furnace takes strong deoxidization technique first, and 290 ~ 310m of aluminum steel is added, and 15min before refining is added Secondary slag material adjusts electric current to maximum value, be rapidly heated slag making, and molten steel is changed into reduction atmosphere by oxidation atmosphere into molten steel It encloses；
B, when liquid steel temperature reaches 1590 DEG C, after scorification is saturating, argon flow is adjusted to 1000NL/min, strong Argon stirring 5min quickly forms white slag, purifies molten steel, and phosphorus content in sampling confirmation molten steel controls molten steel phosphorus content≤0.003%；
C, after molten steel phosphorus content≤0.003%, carbon dust 1.0 ~ 1.5kg/t molten steel is first added in molten steel, is then closed Molten steel composition is adjusted to target component, while strengthening slag making effect by aurification, and argon blowing rate is controlled in 200 ~ 300N//min, really The white slag is protected to hold time in 30min or more.
Preferably, the secondary slag material is 9 ~ 10kg/t of lime molten steel, 1.5 ~ 2.5kg/t of Fluorite pellet molten steel and calcium carbide 0 ~ 1.2kg/t molten steel.
Preferably, the argon flow for continuing Argon described in step S6 is controlled in 150 ~ 200NL/min.
Compared with prior art, the ultralow phosphorus of the present invention faces the mentality of designing of the production method of hydrogen steel and has the beneficial effect that:
The present invention faces a kind of production method of the technical requirements exploitation of hydrogen steel for ultralow phosphorus, faces hydrogen especially suitable for production Steel Q345R successively includes molten iron pretreatment, LD converter smelting, a LF refining, takes off with hydrogen steel 15GrMoR, the production method is faced Slag treatment, secondary LF refining, VD is vacuum-treated and continuous casting, in which:
1) using KR method carry out desulfurizing iron, it is existing research shows that KR desulfurization effect by molten iron temperature, molten steel sulfur content, The influence of mixing time, blender rotation speed and desulfurizing agent additional amount etc., wherein influence phase of the molten iron temperature to desulfurization effect When big, in the identical situation of other conditions, molten iron temperature is higher, then desulfurization effect is better；Desulfurization degree is with desulfurizing agent additional amount Increase and increase, but after additional amount reaches a certain amount of, do not worked to desulfurization；Extend mixing time and accelerates stirring rotation Rotary speed can also improve desulfurization effect, but will increase processing cost accordingly, so that hot metal temperature drop is accelerated.Comprehensively consider into Originally, the factors such as desulfurization desired effect of steel grade, in conjunction with the initial sulfur content 0.035% ~ 0.045% of molten iron of the present invention, molten iron is added 75 ~ 80 tons of amount determines that the rotation speed of stirring-head is 80 ~ 85r/min, and desulfurizing agent calcium oxide additional amount is 450 ~ 500kg, temperature Not less than 1350 DEG C, sulfur content of hot metal≤0.010%, temperature is preferably 1360 ~ 1370 DEG C；
2) present invention steel-making dephosphorization is carried out in the case where aoxidizing atmosphere, takes low-carbon low-phosphor to tap when LD converter is smelted, although LF refining link also can build oxidation atmosphere, but oxidation atmosphere usually not converter link is strong, i.e. refining link dephosphorizing capacity It is limited, therefore converter terminal must take off phosphorus to certain condition, just can ensure that can take off phosphorus after molten steel crosses refining link to expection Level, long-term shop practice production show that the control of converter tapping phosphorus can meet steel grade requirement below 0.012%.Meanwhile being Create conditions to refining dephosphorization, it is desirable that converter terminal taps carbon control between 0.02-0.04%, it is ensured that molten steel oxidation compared with By force.Moreover, any slag material, alloy and deoxidier is not added into molten steel in tapping process, it is ensured that refining link Molten steel carbon, phosphorus content are suitable, and oxidisability is stronger, improve refining dephosphorization rate.Amid all these factors, the present invention is in LD converter link control Oxygen content >=1000ppm processed, takes peroxidating to tap, strict control molten steel end phosphorus content≤0.012%, and carbon content 0.02% ~ 0.04%；
3) LF refining: molten steel phosphorus content≤0.012% after converter smelting needs to make oxidizing slag dephosphorization in this link, Therefore molten steel is added without any deoxidier in this link, the slag material of addition is lime, iron scale and Fluorite pellet, and controls institute Carbon content≤1.0% of slag material is stated, silicone content≤1.0% deoxygenation occurs to avoid this dvielement, respectively in smelting process Slag material primary chemical analysis ingredient content is as follows:
,
In this smelting process, the chemical reaction that steel slag mainly occurs in ladle is as follows:
3CaO+5FeO+2[P]=3CaO·P2O5+ 5 [Fe],
From being chemically reacted above it is found that needing to improve the oxidation in slag to allow chemical reaction equilibrium to carry out to positive direction Calcium content and iron oxide content.Therefore lime is added in slagging process and is mainly used to improve CaO content in slag by the present invention, improves Basicity, this steel grade smelting process basicity of slag control between 4.5-5.5；Slag material iron scale is mainly used to increase in slag FeO content；Fluorite pellet is mainly to increase the mobility of slag, improves reaction efficiency, increases dephosphorization effect.It is well known that making steel Journey dephosphorization is exothermic reaction, therefore temperature is also to influence the key factor of dephosphorization effect, refines link dephosphorization temperature compared to converter Link is easier accurate control, refining link should ensure suitable temperature can will be slag melting, while also to avoid temperature mistake Height influences the progress of dephosphorisation reaction.By constantly groping and practice summary, obtaining the refining optimal dephosphorization temperature of link should be controlled Between 1575-1585 DEG C, this stage lime adding amount is 7 ~ 8kg/t molten steel, and iron scale additional amount is 4 ~ 5kg/t molten steel, Fluorite pellet additional amount is 2 ~ 3.5kg/t molten steel, is practiced in production according to this smelting process, by 3 sampling analyses below, steel Phosphorus content is maintained between 0.002%-0.003% in water, and initial refining dephosphorization desired effect reaches at this time.When phosphorus content in molten steel When reaching target value, slag skimming process is taken, molten steel is hung to station of skimming, takes off the slag blanket of clean molten steel surface, it is certain in production Ensure to skim thoroughly, the oxidisability quantity of slag palpus≤4.0kg/t molten steel on liquid steel level is controlled in practice, when avoiding double refining Reduction atmosphere the phosphorus in slag is restored in molten steel again, the slag skimming process of this link is the entire key step for smelting link Suddenly；
4) secondary LF refining: molten steel is hung to LF refining again and carries out double refining by initial refining dephosphorization and after skimming It smelts, is substantially carried out composition adjustment and inclusion removal.A, the molten steel for being hung to LF furnace takes strong deoxidization technique first, and aluminum steel adds Enter control in 290 ~ 310m, the Argon of be rapidly heated slag making and big intensity is changed into molten steel from oxidation atmosphere in the short time Restore atmosphere；B, when refining process temperature reaches 1590 DEG C, after the quantity of slagization is saturating, abundant Argon stirring, then sampling confirms molten steel Middle phosphorus content, molten steel phosphorus content can control below 0.003% at this time；C, after phosphorus content is suitable, alloying is carried out, until Molten steel composition is adjusted to target component, hydrogen steel Q345R is faced in production need to be added low carbon manganese steel and silicomanganese progress alloying, and production is faced Hydrogen steel 15GrMoR need to be added low carbon manganese steel, silicomanganese, low-carbon ferrochromium and molybdenum-iron and carry out alloying, and each raw material and its specific dosage are Those skilled in the art can be logical according to the ingredient and content range of target product (face hydrogen steel Q345R and face hydrogen steel 15GrMoR) Routine experiment adjustment is crossed to obtain；This stage needs to strengthen refining slag making effect simultaneously, it is ensured that refining link white slag is held time 30min or more controls suitable Argon intensity, improves inclusion removal effect；
5) VD is vacuum-treated: being carried out in VD vacuum drying oven during this, vacuum pressure maintaining period vacuum degree must be maintained at Maxwell Vacuscope measures 67Pa hereinafter, the dwell time 18 minutes, and pressure maintaining period must assure that Argon intensity is larger, and it is good that molten steel seethes effect Good, production practices show that argon flow control in 150 ~ 200NL/min, makes the naked eye diameter in molten steel face in 600mm or more, in fact Show good degassing, desulfurization and goes field trash effect.
Shown by commercial test results complete using HIC the and SSCC performance that ultralow phosphorus faces hydrogen steel obtained by this production method Full up foot GB/T8650-2006 and GB/T4157-2006 standard requirements, steel plate chemical composition stability；Harmful chemical component phosphorus and Sulfur content is lower；Non-metallic inclusion control is good；Slab quality is good, faces hydrogen steel Q345R for ultralow phosphorus and ultralow phosphorus faces hydrogen The industrial production of steel 15GrMoR provides smelting process method.
Specific embodiment
For a better understanding of the present invention, the contents of the present invention, but this hair are further fairly set out below with reference to embodiment Bright protection content is not limited solely to the following examples.In the following description, give a large amount of concrete details so as to More thorough understanding of the invention is provided.It will be apparent, however, to one skilled in the art that the present invention can be with It is carried out without one or more of these details.
Embodiment 1
A kind of ultralow phosphorus faces the production method of hydrogen steel, comprising the following steps:
Step S1: molten iron pretreatment, molten iron is after KR method desulfurization process, and temperature is 1350 DEG C, sulfur content 0.010%；This mistake Cheng Zhong, the initial sulfur content of molten iron are 0.039%, and the rotation speed of stirring-head is 80r/min, and desulfurizing agent calcium oxide additional amount is 450kg；
Step S2:LD converter smelting, converter charge weight are 105 tons, wherein it 80 tons of molten iron, 25 tons of steel scrap, is smelted, In smelting process, control oxygen content is 1000ppm, and the rifle position that blows early period control exists in 1.3m, middle and later periods blowing rifle position control Between 1.0m, one fall temperature be 1550 DEG C, point blow the time control within 2min, point blow number 2 times, converter smelting endpoint, steel Carbon content 0.04% in water, phosphorus content 0.012%, not killing, slag material and alloy during this, and without Argon Technique, tapping finish, and argon station of the molten steel after converter carries out thermometric, and temperature is 1600 DEG C, sampling；
Molten steel is hung to refining furnace and carries out initial refining by S3: LF refining of step, and measuring temperature is 1579 DEG C, this mistake Molten steel not killing in journey passes through high hopper and lime 8kg/t molten steel, iron scale 5kg/t molten steel, Fluorite pellet is added 3.0kg/t molten steel, controls carbon content 0.7%, and silicone content 1.0% adjusts electric current to maximum value, is rapidly heated, when liquid steel temperature liter When to 1585 DEG C, electrode is lifted, argon flow is adjusted to 1000NL/min, strong Argon 5min, sampling analysis, molten steel phosphorus content 0.002 ~ 0.003%, reach a LF refining dephosphorization controlling value；
The main chemical compositions of lime, iron scale and Fluorite pellet as shown in the table below:
,
Step S4: taking off Slag treatment, and molten steel is hung to station of skimming and is skimmed, and controls the oxidisability quantity of slag on liquid steel level ≤ 4.0kg/t molten steel avoids the reduction atmosphere of secondary LF refining from being restored to the phosphorus in slag in molten steel again；
Step S5: secondary LF refining, molten steel are hung to LF furnace again and carry out double refining, to adjust molten steel composition and removal folder Sundries specifically sequentially includes the following steps:
A, the molten steel for being hung to LF furnace takes strong deoxidization technique first, and aluminum steel 310m is added, and lime is added in 15min before refining 9.4kg/t molten steel, Fluorite pellet 1.5kg/t molten steel, calcium carbide 1.2kg/t molten steel, adjustment electric current to maximum value, be rapidly heated slag making, Molten steel is changed into reduction atmosphere by oxidation atmosphere；
B, when liquid steel temperature reaches 1590 DEG C, after scorification is saturating, argon flow is adjusted to 1000NL/min, strong Argon stirring 5min quickly forms white slag, purifies molten steel, and phosphorus content in sampling confirmation molten steel controls molten steel phosphorus content≤0.003%；
C, after molten steel phosphorus content≤0.003%, carbon dust 1.2kg/t molten steel is first added in molten steel, then carry out alloying, Molten steel composition is adjusted to target component, while strengthening slag making effect, argon blowing rate is controlled in 250N//min, it is ensured that described white Slag is held time in 30min or more；
After composition adjustment, temperature rises to 1620 DEG C, and secondary LF refining total time control is within 55min, it is ensured that at Divide uniform Molten Steel Cleanliness high, closes argon gas, molten steel is hung to VD furnace；
Step S6:VD is vacuum-treated, and molten steel is hung to VD furnace, and thermometric is 1610 DEG C, is vacuumized, Maxwell vacuscope measures vacuum 67Pa is spent, the dwell time 18 minutes, argon flow control made the naked eye diameter in molten steel face exist in 180NL/min in pressure maintaining period 600mm or more, breaking air temperature degree is 1565 DEG C, and determining hydrogen is 1.21ppm, and argon flow is adjusted to 50NL/min, soft blow argon 8min, temperature Degree closes argon gas, into continuous casting working procedure to 1557 DEG C；
Step S7: continuous casting, the middle packet degree of superheat are 25 DEG C, and pulling rate 0.85m/min obtains slab.
Embodiment 2
A kind of ultralow phosphorus faces the production method of hydrogen steel, comprising the following steps:
Step S1: molten iron pretreatment, molten iron is after KR method desulfurization process, and temperature is 1360 DEG C, sulfur content 0.008%；This mistake Cheng Zhong, the initial sulfur content of molten iron are 0.041%, and the rotation speed of stirring-head is 82r/min, and desulfurizing agent calcium oxide additional amount is 480kg；
Step S2:LD converter smelting, converter charge weight are 100 tons, wherein it 75 tons of molten iron, 25 tons of steel scrap, is smelted, In smelting process, control oxygen content is 1040ppm, and the rifle position that blows early period control exists in 1.3m, middle and later periods blowing rifle position control Between 0.9m, one fall temperature be 1550 DEG C, point blow the time control within 2min, point blow number 1 time, converter smelting endpoint, steel Carbon content 0.03% in water, phosphorus content 0.010%, not killing, slag material and alloy during this, and without Argon Technique, tapping finish, and argon station of the molten steel after converter carries out thermometric, and temperature is 1602 DEG C, sampling；
Molten steel is hung to refining furnace and carries out initial refining by S3: LF refining of step, and measuring temperature is 1579 DEG C, this mistake Molten steel not killing in journey passes through high hopper and lime 7.5kg/t molten steel, iron scale 4.3kg/t molten steel, Fluorite pellet is added 2.6kg/t molten steel, controls carbon content 0.8%, and silicone content 0.9% adjusts electric current to maximum value, is rapidly heated, when liquid steel temperature liter When to 1585 DEG C, electrode is lifted, argon flow is adjusted to 1000NL/min, strong Argon 5min, sampling analysis, molten steel phosphorus content 0.002 ~ 0.003%, reach a LF refining dephosphorization controlling value；
The main chemical compositions of lime, iron scale and Fluorite pellet as shown in the table below:
,
Step S4: taking off Slag treatment, and molten steel is hung to station of skimming and is skimmed, and controls the oxidisability quantity of slag on liquid steel level ≤ 4.0kg/t molten steel avoids the reduction atmosphere of secondary LF refining from being restored to the phosphorus in slag in molten steel again；
Step S5: secondary LF refining, molten steel are hung to LF furnace again and carry out double refining, to adjust molten steel composition and removal folder Sundries specifically sequentially includes the following steps:
A, the molten steel for being hung to LF furnace takes strong deoxidization technique first, and aluminum steel 300m is added, and lime is added in 15min before refining 9kg/t molten steel, Fluorite pellet 2.0kg/t molten steel, calcium carbide are 1.0kg/t molten steel, and adjustment electric current to maximum value, be rapidly heated slag making, Molten steel is changed into reduction atmosphere by oxidation atmosphere；
B, when liquid steel temperature reaches 1590 DEG C, after scorification is saturating, argon flow is adjusted to 1000NL/min, strong Argon stirring 5min quickly forms white slag, purifies molten steel, and phosphorus content in sampling confirmation molten steel controls molten steel phosphorus content≤0.003%；
C, after molten steel phosphorus content≤0.003%, carbon dust 1.2kg/t molten steel is first added in molten steel, then carry out alloying, Molten steel composition is adjusted to target component, while strengthening slag making effect, argon blowing rate is controlled in 280N//min, it is ensured that described white Slag is held time in 30min or more；
After composition adjustment, temperature rises to 1620 DEG C, and secondary LF refining total time control is within 55min, it is ensured that at Divide uniform Molten Steel Cleanliness high, closes argon gas, molten steel is hung to VD furnace；
Step S6:VD is vacuum-treated, and molten steel is hung to VD furnace, and thermometric is 1610 DEG C, is vacuumized, Maxwell vacuscope measures vacuum 65Pa is spent, the dwell time 18 minutes, argon flow control made the naked eye diameter in molten steel face exist in 150NL/min in pressure maintaining period 600mm or more, breaking air temperature degree is 1565 DEG C, and determining hydrogen is 1.21ppm, and argon flow is adjusted to 50NL/min, soft blow argon 8min, temperature Degree closes argon gas, into continuous casting working procedure to 1557 DEG C；
Step S7: continuous casting, the middle packet degree of superheat are 25 DEG C, and pulling rate 0.85m/min obtains slab.
Embodiment 3
A kind of ultralow phosphorus faces the production method of hydrogen steel, comprising the following steps:
Step S1: molten iron pretreatment, molten iron is after KR method desulfurization process, and temperature is 1365 DEG C, sulfur content 0.006%；This mistake Cheng Zhong, the initial sulfur content of molten iron are 0.041%, and the rotation speed of stirring-head is 83r/min, and desulfurizing agent calcium oxide additional amount is 465kg；
Step S2:LD converter smelting, converter charge weight are 100 tons, wherein it 80 tons of molten iron, 20 tons of steel scrap, is smelted, In smelting process, oxygen content 1020ppm is controlled, in 1.3m, the middle and later periods blows rifle position control in 1.1m for the rifle position that blows early period control Between, one to fall temperature be 1550 DEG C, and point blows time control within 2min, and point is blown number 2 times, converter smelting endpoint, in molten steel Carbon content 0.03%, phosphorus content 0.011%, not killing, slag material and alloy during this, and without gon technics, Tapping finishes, and argon station of the molten steel after converter carries out thermometric, and temperature is 1605 DEG C, sampling；
Molten steel is hung to refining furnace and carries out initial refining by S3: LF refining of step, and measuring temperature is 1579 DEG C, this mistake Molten steel not killing in journey passes through high hopper and lime 7kg/t molten steel, iron scale 4kg/t molten steel, Fluorite pellet 2kg/ is added T molten steel, controls carbon content 1.0%, and silicone content 0.8% adjusts electric current to maximum value, is rapidly heated, when liquid steel temperature rises to 1585 DEG C when, lift electrode, argon flow is adjusted to 1000NL/min, strong Argon 5min, sampling analysis, molten steel phosphorus content 0.002 ~ 0.003%, reach a LF refining dephosphorization controlling value；
The main chemical compositions of lime, iron scale and Fluorite pellet as shown in the table below:
,
Step S4: taking off Slag treatment, and molten steel is hung to station of skimming and is skimmed, and controls the oxidisability quantity of slag on liquid steel level ≤ 4.0kg/t molten steel avoids the reduction atmosphere of secondary LF refining from being restored to the phosphorus in slag in molten steel again；
Step S5: secondary LF refining, molten steel are hung to LF furnace again and carry out double refining, to adjust molten steel composition and removal folder Sundries specifically sequentially includes the following steps:
A, the molten steel for being hung to LF furnace takes strong deoxidization technique first, and aluminum steel 305m is added, and lime is added in 15min before refining 9.6kg/t molten steel, Fluorite pellet 2.3kg/t molten steel, calcium carbide are 0.8kg/t molten steel, adjust electric current to maximum value, are rapidly heated and make Molten steel is changed into reduction atmosphere by oxidation atmosphere by slag；
B, when liquid steel temperature reaches 1590 DEG C, after scorification is saturating, argon flow is adjusted to 1000NL/min, strong Argon stirring 5min quickly forms white slag, purifies molten steel, and phosphorus content in sampling confirmation molten steel controls molten steel phosphorus content≤0.003%；
C, after molten steel phosphorus content≤0.003%, carbon dust 1.0kg/t molten steel is first added in molten steel, then carry out alloying, Molten steel composition is adjusted to target component, while strengthening slag making effect, argon blowing rate is controlled in 300N//min, it is ensured that described white Slag is held time in 30min or more；
After composition adjustment, temperature rises to 1620 DEG C, and secondary LF refining total time control is within 55min, it is ensured that at Divide uniform Molten Steel Cleanliness high, closes argon gas, molten steel is hung to VD furnace；
Step S6:VD is vacuum-treated, and molten steel is hung to VD furnace, and thermometric is 1610 DEG C, is vacuumized, Maxwell vacuscope measures vacuum 63Pa is spent, the dwell time 18 minutes, argon flow control made the naked eye diameter in molten steel face exist in 190NL/min in pressure maintaining period 600mm or more, breaking air temperature degree is 1565 DEG C, and determining hydrogen is 1.21ppm, and argon flow is adjusted to 50NL/min, soft blow argon 8min, temperature Degree closes argon gas, into continuous casting working procedure to 1557 DEG C；
Step S7: continuous casting, the middle packet degree of superheat are 20 DEG C, and pulling rate 0.85m/min obtains slab.
Embodiment 4
A kind of ultralow phosphorus faces the production method of hydrogen steel, comprising the following steps:
Step S1: molten iron pretreatment, molten iron is after KR method desulfurization process, and temperature is 1370 DEG C, sulfur content 0.005%；This mistake Cheng Zhong, the initial sulfur content of molten iron are 0.039%, and the rotation speed of stirring-head is 83r/min, and desulfurizing agent calcium oxide additional amount is 492kg；
Step S2:LD converter smelting, converter charge weight are 100 tons, wherein it 77 tons of molten iron, 23 tons of steel scrap, is smelted, In smelting process, oxygen content 1100ppm is controlled, in 1.3m, the middle and later periods blows rifle position control in 1.0m for the rifle position that blows early period control Between, one to fall temperature be 1550 DEG C, and point blows time control within 2min, and point is blown number 2 times, converter smelting endpoint, in molten steel Carbon content 0.02%, phosphorus content 0.010%, not killing, slag material and alloy during this, and without gon technics, Tapping finishes, and argon station of the molten steel after converter carries out thermometric, and temperature is 1602 DEG C, sampling；
Molten steel is hung to refining furnace and carries out initial refining by S3: LF refining of step, and measuring temperature is 1579 DEG C, this mistake Molten steel not killing in journey passes through high hopper and lime 7.8kg/t molten steel, iron scale 4.8kg/t molten steel, Fluorite pellet is added 3.2kg/t molten steel, controls carbon content 0.9%, and silicone content 1.0% adjusts electric current to maximum value, is rapidly heated, when liquid steel temperature liter When to 1585 DEG C, electrode is lifted, argon flow is adjusted to 1000NL/min, strong Argon 5min, sampling analysis, molten steel phosphorus content 0.002 ~ 0.003%, reach a LF refining dephosphorization controlling value；
The main chemical compositions of lime, iron scale and Fluorite pellet as shown in the table below:
,
Step S4: taking off Slag treatment, and molten steel is hung to station of skimming and is skimmed, and controls the oxidisability quantity of slag on liquid steel level ≤ 4.0kg/t molten steel avoids the reduction atmosphere of secondary LF refining from being restored to the phosphorus in slag in molten steel again；
Step S5: secondary LF refining, molten steel are hung to LF furnace again and carry out double refining, to adjust molten steel composition and removal folder Sundries specifically sequentially includes the following steps:
A, the molten steel for being hung to LF furnace takes strong deoxidization technique first, and aluminum steel 295m is added, and lime is added in 15min before refining 9.2kg/t molten steel, Fluorite pellet 2.5kg/t molten steel, calcium carbide are 1.0kg/t molten steel, adjust electric current to maximum value, are rapidly heated and make Molten steel is changed into reduction atmosphere by oxidation atmosphere by slag；
B, when liquid steel temperature reaches 1590 DEG C, after scorification is saturating, argon flow is adjusted to 1000NL/min, strong Argon stirring 5min quickly forms white slag, purifies molten steel, and phosphorus content in sampling confirmation molten steel controls molten steel phosphorus content≤0.003%；
C, after molten steel phosphorus content≤0.003%, carbon dust 1.5kg/t molten steel is first added in molten steel, then carry out alloying, Molten steel composition is adjusted to target component, while strengthening slag making effect, argon blowing rate is controlled in 200N//min, it is ensured that described white Slag is held time in 30min or more；
After composition adjustment, temperature rises to 1620 DEG C, and secondary LF refining total time control is within 55min, it is ensured that at Divide uniform Molten Steel Cleanliness high, closes argon gas, molten steel is hung to VD furnace；
Step S6:VD is vacuum-treated, and molten steel is hung to VD furnace, and thermometric is 1610 DEG C, is vacuumized, Maxwell vacuscope measures vacuum 67Pa is spent, the dwell time 18 minutes, argon flow control made the naked eye diameter in molten steel face exist in 200NL/min in pressure maintaining period 600mm or more, breaking air temperature degree is 1565 DEG C, and determining hydrogen is 1.21ppm, and argon flow is adjusted to 50NL/min, soft blow argon 8min, temperature Degree closes argon gas, into continuous casting working procedure to 1557 DEG C；
Step S7: continuous casting, the middle packet degree of superheat are 25 DEG C, and pulling rate 0.85m/min obtains slab.
Embodiment 5
A kind of ultralow phosphorus faces the production method of hydrogen steel, comprising the following steps:
Step S1: molten iron pretreatment, molten iron is after KR method desulfurization process, and temperature is 1380 DEG C, sulfur content 0.009%；This mistake Cheng Zhong, the initial sulfur content of molten iron are 0.040%, and the rotation speed of stirring-head is 85r/min, and desulfurizing agent calcium oxide additional amount is 500kg；
Step S2:LD converter smelting, converter charge weight are 100 tons, wherein it 75 tons of molten iron, 25 tons of steel scrap, is smelted, In smelting process, oxygen content 1050ppm is controlled, in 1.3m, the middle and later periods blows rifle position control in 1.0m for the rifle position that blows early period control Between, one to fall temperature be 1550 DEG C, and point blows time control within 2min, and point is blown number 2 times, converter smelting endpoint, in molten steel Carbon content 0.03%, phosphorus content 0.012%, not killing, slag material and alloy during this, and without gon technics, Tapping finishes, and argon station of the molten steel after converter carries out thermometric, and temperature is 1605 DEG C, sampling；
Molten steel is hung to refining furnace and carries out initial refining by S3: LF refining of step, and measuring temperature is 1580 DEG C, this mistake Molten steel not killing in journey passes through high hopper and lime 7kg/t molten steel, iron scale 4kg/t molten steel, Fluorite pellet 2kg/ is added T molten steel, controls carbon content 1.0%, and silicone content 1.0% adjusts electric current to maximum value, is rapidly heated, when liquid steel temperature rises to 1585 DEG C when, lift electrode, argon flow is adjusted to 1000NL/min, strong Argon 5min, sampling analysis, molten steel phosphorus content 0.002 ~ 0.003%, reach a LF refining dephosphorization controlling value；
The main chemical compositions of lime, iron scale and Fluorite pellet as shown in the table below:
,
Step S4: taking off Slag treatment, and molten steel is hung to station of skimming and is skimmed, and controls the oxidisability quantity of slag on liquid steel level ≤ 4.0kg/t molten steel avoids the reduction atmosphere of secondary LF refining from being restored to the phosphorus in slag in molten steel again；
Step S5: secondary LF refining, molten steel are hung to LF furnace again and carry out double refining, to adjust molten steel composition and removal folder Sundries specifically sequentially includes the following steps:
A, the molten steel for being hung to LF furnace takes strong deoxidization technique first, and aluminum steel 300m is added, and lime is added in 15min before refining 10kg/t molten steel, Fluorite pellet 1.8kg/t molten steel, calcium carbide are 1.0kg/t molten steel, and adjustment electric current to maximum value, be rapidly heated slag making, Molten steel is changed into reduction atmosphere by oxidation atmosphere；
B, when liquid steel temperature reaches 1590 DEG C, after scorification is saturating, argon flow is adjusted to 1000NL/min, strong Argon stirring 5min quickly forms white slag, purifies molten steel, and phosphorus content in sampling confirmation molten steel controls molten steel phosphorus content≤0.003%；
C, after molten steel phosphorus content≤0.003%, carbon dust 1.4kg/t molten steel is first added in molten steel, then carry out alloying, Molten steel composition is adjusted to target component, while strengthening slag making effect, argon blowing rate is controlled in 220N//min, it is ensured that described white Slag is held time in 30min or more；
After composition adjustment, temperature rises to 1620 DEG C, and secondary LF refining total time control is within 55min, it is ensured that at Divide uniform Molten Steel Cleanliness high, closes argon gas, molten steel is hung to VD furnace；
Step S6:VD is vacuum-treated, and molten steel is hung to VD furnace, and thermometric is 1610 DEG C, is vacuumized, Maxwell vacuscope measures vacuum 65Pa is spent, the dwell time 18 minutes, argon flow control made the naked eye diameter in molten steel face exist in 180NL/min in pressure maintaining period 600mm or more, breaking air temperature degree is 1565 DEG C, and determining hydrogen is 1.21ppm, and argon flow is adjusted to 50NL/min, soft blow argon 8min, temperature Degree closes argon gas, into continuous casting working procedure to 1557 DEG C；
Step S7: continuous casting, 23 DEG C of the middle packet degree of superheat, pulling rate 0.85m/min obtain slab.
Comparative example 1
Ultralow phosphorus described in this comparative example 1 faces the production method of hydrogen steel, substantially the same manner as Example 1, and institute is different :
Step S4 is omitted, step S5 is adjusted to step S4 ', step S6 is adjusted to step S5 ', in which: step S4 ' is the same as real The step S5 of example 1 is applied, step S5 ' is repeated no more with the step S6 of embodiment 1.
Comparative example 2
Ultralow phosphorus described in this comparative example 2 faces the production method of hydrogen steel, substantially the same manner as Example 1, and institute is different :
Step S3 and step S4 is omitted, step S5 is adjusted to step S3 ', step S6 is adjusted to step S4 ', wherein step Rapid S3 ' specifically:
Molten steel is hung to LF furnace to refine, is specifically sequentially included the following steps:
A, the molten steel for being hung to LF furnace takes strong deoxidization technique first, and aluminum steel 310m is added, and lime is added in 15min before refining 17.4kg/t molten steel, Fluorite pellet 4.5kg/t molten steel, calcium carbide 1.2kg/t molten steel, adjustment electric current to maximum value, be rapidly heated slag making, Molten steel is changed into reduction atmosphere by oxidation atmosphere；
B, when liquid steel temperature reaches 1590 DEG C, after scorification is saturating, argon flow is adjusted to 1000NL/min, strong Argon stirring 5min quickly forms white slag, purifies molten steel, phosphorus content in sampling confirmation molten steel；
C, after molten steel phosphorus content≤0.007%, carbon dust 1.2kg/t molten steel is first added in molten steel, then carry out alloying, Molten steel composition is adjusted to target component, while strengthening slag making effect, argon blowing rate is controlled in 250N//min, it is ensured that described white Slag is held time in 30min or more；
After composition adjustment, temperature rises to 1620 DEG C, and LF refining total time controls within 55min, it is ensured that ingredient is equal Uniform Molten Steel Cleanliness is high, closes argon gas, molten steel is hung to VD furnace；
Step S4 ' is repeated no more with the step S6 of embodiment 1.
1 ~ embodiment of above-described embodiment 5,1 ~ 2 gained slab of comparative example successively pass through following steps, can be obtained finished product and face Hydrogen steel steel plate:
1) slab sampling observation cleaning: heap cold 48 hours after slab cutting, then de-stacking carries out sampling observation cleaning to casting billet surface, really Protecting casting billet surface does not have the defects of crackle, stomata and stammerer；
2) slab heating rolling: the slab for inspecting qualification by random samples enters heating furnace by roller-way and is heated, and 10 DEG C of heating speed/ Min, temperature rise between 1190 ~ 1260 DEG C, keep the temperature 2h, are rolled after heating and thermal insulation, the operation of rolling takes high temperature low The big soft reduction process of speed；
3) steel plate heap is cold: rolling rear steel plate and enters burial pit to carry out heap cold, reaches and eliminate internal stress and spread dehydrogenation Effect；
4) after steel plate finishing normalizing line be heat-treated: after steel plate heap is cold de-stacking carry out finishing, the steel plate that finishing terminates into Enter normalizing line and carries out heat treatment process；
5) enter warehouse for finished product after flaw detection, outer inspection, performance are qualified: being detected a flaw after heat treatment to steel plate, outer inspection and sampling inspection Performance is surveyed, all enters warehouse for finished product after qualification.
It is respectively obtained using aforementioned production method and faces hydrogen steel Q345R and 15GrMoR, obtained to by embodiment 1, comparative example 1 ~ 2 Face hydrogen the steel Q345R and 15GrMoR obtained carries out following analysis and effect assessment.
1, ingredient is examined: facing hydrogen steel Q345R and 15GrMoR and carry out ingredient inspection embodiment 1,1 ~ 2 gained of comparative example；It is real Apply example 1, the gained of comparative example 1 ~ 2 faces the actual constituent average value of hydrogen steel Q345R and is shown in Table 1-1, embodiment 1,1 ~ 2 gained of comparative example face The actual constituent average value of hydrogen steel 15GrMoR is shown in Table 1-2.
Table 1-1 faces the practical chemical component average value of hydrogen steel Q345R (mass fraction percentage, wt%)
,
Table 1-2 faces the practical chemical component average value of hydrogen steel 15GrMoR (mass fraction percentage, wt%)
,
Table 1-1 and table 1-2's the result shows that: the control of steel grade each element obtained by 1 production method of embodiment is good, especially has Evil element phosphor and sulfur content control are extremely low, steel grade harmful element p and s content control effect obtained by 1 ~ 2 production method of comparative example It is bad.
2, mechanical properties test: face hydrogen the steel Q345R and 15GrMoR that embodiment 1 ~ 5, comparative example 1 ~ 2 are produced carry out power Service check is learned, inspection result is shown in Table respectively shown in 2-1 and 2-2.
Table 2-1 faces the mechanical property of hydrogen steel Q345R
,
Table 2-2 faces the mechanical property of hydrogen steel 15GrMoR
。
Wherein, yield strength test method: refering to GB/T228.1-2010；Tensile strength test method: refering to GB/ T228.1-2010；Elongation after fracture test method: refering to GB/T228.1-2010；Ballistic work test method: refering to GB/T229- 2007；Brinell hardness test method: GBT231.1-2009；180 ° of test methods of bend test: refering to GB/T232-2010.
3, nonmetal inclusion analyte detection: appoint take 20 batches by embodiment 1, comparative example 1 ~ 2 produce face hydrogen steel Q345R and 15GrMoR carries out being mingled with analyte detection, and testing result is shown in Table respectively shown in 3-1 and 3-2.
Table 3-1 faces hydrogen steel Q345R non-metallic inclusion testing result
,
Table 3-2 faces hydrogen steel 15GrMoR non-metallic inclusion testing result
。
Table 3-1,3-2 the result shows that, the ultralow non-metallic inclusion rank faced in hydrogen steel obtained by embodiment 1 production method Lower, highest level is 0.5 grade, and content is less, and the A class and C class being especially affected to the hic resistance of steel and SSCC performance are pressed from both sides In miscellaneous, 0.5 grade or more to be mingled with accounting very low, this shows that smelting process control is good, and the cleanliness of steel is higher；And comparative example 1 Increase with the non-metallic inclusion rank faced in hydrogen steel obtained by comparative example 2, specifically, facing in hydrogen steel using obtained by comparative example 1 Non-metallic inclusion rank is up to 1.0 grades, and all kinds of inclusion contents increase；Face in hydrogen steel using obtained by comparative example 2 Non-metallic inclusion rank is up to 1.5 grades, and all kinds of inclusion contents obviously increase, and illustrates that comparative example 1 ~ 2 adjusts this hair The control effect for facing hydrogen nonmetallic inclusionsin steel is declined after bright production method.
4, HIC and SSCC service check: appoint and 6 batches is taken to be obtained by embodiment 1,1 ~ 2 production method of comparative example and faced hydrogen steel Q345R and 15GrMoR steel plate is respectively classified into two groups, then carries out HIC and SSCC service check respectively to every group.
1) HIC is examined: according to GB/T8650-2006 " pipe line steel and pressure vessel steel resistance against hydrogen cracking assessment method " standard Middle solution A requirement, prepares 5%NaCl+0.5%CH3COOH+ saturated hydrog en sulphide solution, to facing hydrogen steel Q345R and 15GrMoR Steel plate carries out anti-hydrogen induced cracking (HIC) performance detection.When starting, the pH test value of testing liquid is 3.1, solution after test PH test value is 3.7.After test, amplifies 100 times by testing standard requirement and section is checked, totally 3 samples, each sample 3 detection faces inspections are taken, crack-sensitivity rate (CSR), crack length Sensitivity rate (CLR) and the crack thickness Sensitivity rate of test specimen are evaluated (CTR), occurrence is respectively as shown in table 4-1 and 4-2.
Table 4-1 faces the HIC test result of hydrogen steel Q345R
,
Table 4-2 faces the HIC test result of hydrogen steel 15GrMoR
。
Table 4-1 and table 4-2's the result shows that, face hydrogen steel Q345R and 15GrMoR using obtained by production method of the present invention HIC performance fully meets GB/T8650-2006 standard requirements.Using facing the crack-sensitivity rate of hydrogen steel Q345R obtained by comparative example 1 not (CSR≤0.5%) is met the requirements of the standard, using the crack thickness Sensitivity rate and crack-sensitivity for facing hydrogen steel Q345R obtained by comparative example 2 Rate does not meet standard requirements (CTR≤1.5%, CSR≤0.5%), illustrate to change production method of the present invention to face hydrogen steel Q345R and The HIC performance of 15GrMoR, which has, to be significantly affected.
2) SSCC is examined: according to GB/T4157-2006, " metal anti-special shape environmental cracking in hydrogen-sulfide environmental is tested Room test " solution A requirement in standard, prepare H2The 5%NaCl+0.5%CH of S saturation3COOH distills water mixed solution, using side The tensile sample that method A, i.e. active section diameter are 6.35mm carries out stress corrosion (SSCC) test, and pH value of solution is tested during test Value is no more than 4.0, and test result is as shown in table 5.
Table 5-1 faces the SSCC test result of hydrogen steel Q345R
,
Table 5-2 faces the SSCC test result of hydrogen steel 15GrMoR
。
Table 5-1 and table 5-2's the result shows that, using the method for the present invention hydrogen steel Q345R and 15GrMoR produced of facing SSCC performance fully meets GB/T4157-2006 standard requirements.Using facing the SSCC performance of hydrogen steel Q345R obtained by comparative example 1 not Meet GB/T4157-2006 standard requirements, GB/T4157- is not met using the SSCC performance for facing hydrogen steel Q345R obtained by comparative example 2 2006 standard requirements illustrate that changing production method of the present invention has significant shadow to the SSCC performance for facing hydrogen steel Q345R and 15GrMoR It rings.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, this field is common Other modifications or equivalent replacement that technical staff makes technical solution of the present invention, without departing from technical solution of the present invention Spirit and scope, be intended to be within the scope of the claims of the invention.

Claims (9)

1. the production method that a kind of ultralow phosphorus faces hydrogen steel, it is characterised in that: the following steps are included:
Step S1: molten iron pretreatment, molten iron is after KR method desulfurization process, temperature >=1350 DEG C, sulfur content≤0.010%；
Step S2:LD converter smelting, converter smelting endpoint, carbon content 0.02% ~ 0.04% in molten steel, phosphorus content≤0.012%, this Not killing, slag material and alloy in the process, and without gon technics, tapping finishes, argon station of the molten steel after converter Carry out thermometric；
A slag material is added in S3: LF refining of step, this process, controls carbon content≤1.0% of a slag material, Silicone content≤1.0% adjusts electric current to maximum value, is rapidly heated, when liquid steel temperature rises to 1585 DEG C, lifts electrode, argon gas stream Amount is adjusted to 1000NL/min, strong Argon 5min, sampling analysis, and molten steel phosphorus content 0.002 ~ 0.003% reaches a LF refining Dephosphorization controlling value；
Step S4: taking off Slag treatment, and molten steel is hung to station of skimming and is skimmed, and the oxidisability quantity of slag on control liquid steel level≤ 4.0kg/t molten steel；
Step S5: secondary LF refining, molten steel are hung to LF furnace again and carry out double refining, be mingled with adjusting molten steel composition and removal Object；
Step S6:VD is vacuum-treated, and Maxwell vacuscope measurement of vacuum≤67Pa, the dwell time 18 minutes, pressure maintaining period was lasting Argon makes the naked eye diameter in molten steel face in 600mm or more；
Step S7: continuous casting, the middle packet degree of superheat≤25 DEG C, pulling rate 0.85m/min.
2. the production method that ultralow phosphorus according to claim 1 faces hydrogen steel, it is characterised in that: iron in the molten iron pretreatment The temperature of water is 1360 ~ 1370 DEG C.
3. the production method that ultralow phosphorus according to claim 1 faces hydrogen steel, it is characterised in that: the LD converter smelting process In, in 1.3m, the middle and later periods blows rifle position control between 0.9-1.1m for the rifle position that blows early period control, and one to fall temperature be 1550 DEG C, Point blows time control within 2min, and point blows number≤2 time.
4. the production method that ultralow phosphorus according to claim 1-3 faces hydrogen steel, it is characterised in that: the LD converter In smelting process, oxygen content >=1000ppm is controlled.
5. the production method that ultralow phosphorus according to claim 1 faces hydrogen steel, it is characterised in that: a slag material is stone Ash, iron scale and Fluorite pellet, the lime adding amount are 7 ~ 8kg/t molten steel, and the iron scale additional amount is 4 ~ 5kg/t steel Water, the Fluorite pellet additional amount are 2 ~ 3.5kg/t molten steel.
6. the production method that ultralow phosphorus according to claim 5 faces hydrogen steel, it is characterised in that: contain in the lime CaO90wt%, SiO23wt%, the activity degree of the lime are 300 ~ 350ml；In the iron scale TFe content 86wt% with On；Contain CaF in the Fluorite pellet282wt%, SiO21.3wt%。
7. the production method that ultralow phosphorus according to claim 1 faces hydrogen steel, it is characterised in that: the secondary LF refining is specific It sequentially includes the following steps:
A, the molten steel for being hung to LF furnace takes strong deoxidization technique first, and 290 ~ 310m of aluminum steel is added, and 15min before refining is added secondary Slag material adjusts electric current to maximum value, be rapidly heated slag making, and molten steel is changed into reduction atmosphere by oxidation atmosphere into molten steel；
B, when liquid steel temperature reaches 1590 DEG C, after scorification is saturating, argon flow is adjusted to 1000NL/min, and strong Argon stirs 5min, White slag is quickly formed, molten steel is purified, phosphorus content in sampling confirmation molten steel controls molten steel phosphorus content≤0.003%；
C, after molten steel phosphorus content≤0.003%, carbon dust 1.0 ~ 1.5kg/t molten steel is first added in molten steel, then carries out alloy Change, molten steel composition be adjusted to target component, while strengthening slag making effect, argon blowing rate is controlled in 200 ~ 300N//min, it is ensured that The white slag is held time in 30min or more.
8. the production method that ultralow phosphorus according to claim 7 faces hydrogen steel, it is characterised in that: the secondary slag material is stone Ash 9 ~ 10kg/t molten steel, 1.5 ~ 2.5kg/t of Fluorite pellet molten steel and calcium carbide 0 ~ 1.2kg/t molten steel.
9. the production method that ultralow phosphorus according to claim 1 faces hydrogen steel, it is characterised in that: persistently blown described in step S6 The argon flow of argon is controlled in 150 ~ 200NL/min.
CN201711158046.6A 2017-11-20 2017-11-20 A kind of ultralow phosphorus faces the production method of hydrogen steel Active CN107868900B (en)

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CN109385505B (en) * 2018-09-25 2020-05-12 北京科技大学 Method for obtaining reducing high-alkalinity white slag by vacuum control in VD furnace
CN109161630B (en) * 2018-09-25 2020-07-24 湖南华菱湘潭钢铁有限公司 Smelting method of HIC-resistant pipeline steel
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CN109439832A (en) * 2018-12-11 2019-03-08 南阳汉冶特钢有限公司 A kind of ultralow phosphorus faces the smelting process of hydrogen steel
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