CN1563463A - Manufactring method for smelting stainless steel containing N biphase - Google Patents
Manufactring method for smelting stainless steel containing N biphase Download PDFInfo
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- CN1563463A CN1563463A CN 200410017115 CN200410017115A CN1563463A CN 1563463 A CN1563463 A CN 1563463A CN 200410017115 CN200410017115 CN 200410017115 CN 200410017115 A CN200410017115 A CN 200410017115A CN 1563463 A CN1563463 A CN 1563463A
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Abstract
A method for smelting double-phase with N stain less steel characterizes 1. carrying out the primary smelting according to the return oxygen blowing wethod 2. smelting qualified double stainless steel with N in composition and purity (1) blown temperature is higher than or equal to 1540deg,c (2) carbon elimination: blowing N2, O2 mixed gas for decarbonization and increasing N2 and process the increased temperature O2/N2=4, sampling to regulated the components: when c=0.10%, stop blowing O2 but Ar instead, adding prerecovered stags for 7min, total sample analysis including all stags and adding recovery stags (3) recovery: blowing Ar and forcing to eliminate O, blowing N to increase N, sample analysis, fine adjustment to the composition to get the cast ingot.
Description
Technical field
The present invention relates to stainless smelting of metallurgy industry and casting process, refer in particular to the smelting process of duplex stainless steel.
Background technology
Stainless steel is common steel alloy, generally can be divided into austenitic stainless steel, ferritic stainless steel, Martensite Stainless Steel and duplex stainless steel.So-called duplex stainless steel be in its solid solution structure austenite mutually and ferrite make an appointment and respectively account for about 50%, general content of looking younger needs to reach 30% at least.Duplex stainless steel not only has the excellent in toughness and the weldability of ferritic stainless steel, also have the higher-strength and the anti-chloride stress cracking corrosive nature of austenitic stainless steel concurrently, anti-spot corrosion and anti-stress corrosion performance that it is good, can be at acidic medium, especially life-time service under high chloride ion environment and heavily stressed etching condition is widely used in fields such as oil, ocean and chemical industry.
The basal component of duplex stainless steel is: (Cr content=18～25%, chromium can promote the formation of ferritic phase in the steel and stablize, improve the intergranular corrosion resistance performance of steel Gao Ge.), rich nickel (Ni content=4～7%, Ni is the element that major control balances each other in the duplex stainless steel, help enlarging the austenite phase ratio in the steel, too highly cause austenite phase 〉=50% in the steel, can make the element that more enrichment chromium, molybdenum etc. impel σ fragility to change mutually in the ferritic phase, reduce the toughness of steel; Cross the low ferrite quantity height in the steel that causes, reduce the plasticity and toughness of steel.), (C content≤0.03%, C content is higher in the steel, can lose the balance of phase during welding, causes solidity to corrosion and toughness to descend, and is restricted on using for Ultra-low carbon.), an amount of ferritic phase forming element Mo, W, and an amount of austenite phase forming element N.
In duplex stainless steel, N as austenite phase forming element plays an important role: when cooling off fast in the welding joint heat affected zone, the ferrite that N has promoted high temperature to form down reverses and becomes enough secondary austenites to keep necessary balancing each other, and improves the solidity to corrosion of joint; N can improve the anti-pitting ability of rich nitrogen austenitic phase, averages out with the ferritic phase of rich Cr, Mo, has improved the anti-pitting performance of material monolithic; N can alleviate the difference that elements such as Cr, Ni distribute in two-phase, reduce the proneness of selective corrosion.Just because of these effect unique of N, the research and development that contain the N duplex stainless steel have obtained Iron and Steel Production producer and user's welcome.Comparatively speaking, the N duplex stainless steel that contains American-European and Japan and Korea S steel mill is started to walk early, and production technique is ripe, and it is many that the trade mark also becomes; China then starts late, and not only industrial scale is little, and the trade mark is also more single, and smelting technology still is in the exploratory stage, and especially the Composition Control of C, N difficulty so metallurgical quality is stable inadequately, is not seen the bibliographical information of detailed production method both at home and abroad yet.
In theory, method to stainless steel molten steel nitrogen pick-up (N) has two kinds: a kind of is to add to contain the N alloy, but because it is lower and composition is unstable (composition fluctuation just is bigger) to contain N content in the N alloy (as nitrogenized manganese, chromium nitride etc.), cause the extremely unstable of the N rate of recovery, cause the N content control difficulty of duplex stainless steel finished product, cause product rejection when serious, nitrogenized manganese, chromium nitride etc. contain the price comparison height of N alloy in addition, also are the restraining factors of ordinary production; Another kind is to be blown into nitrogen in molten steel (in the actual production, AOD stove refining early stage mainly is a mixed gas nitrogenous, oxygen, decarburization, nitrogen pick-up on the other hand on the one hand.), the both economical practicality of this method, favourable condition is that N has certain solubleness in molten stainless steel, the price of nitrogen is also relatively more cheap; Difficult point is that molten steel increases the influence that N amount (or taking off the N amount) is subjected to many-sided factor such as sulphur and oxygen level in chromium nickel ratio, carbon equivalent, dividing potential drop, molten steel temperature and the steel of nitrogen in atmosphere, and the bound scope of N content is very narrow in the molten steel, the advanced N duplex stainless steel that contains, the bound scope of N content has only 0.05% (500ppm just, to a concrete N duplex stainless steel steel grade that contains, N content is too high or too low, can influence balancing each other in the steel, influences the performance of steel.), therefore very difficult to the control of nitrogen in steel, the difficulty of producing smelting is very big.Therefore, concerning many key areas that need to use duplex stainless steel of national economy, mostly have to rely on import to solve.
Summary of the invention
The present invention develops a kind of smelting production method of the N of containing duplex stainless steel, adopt the mode of " electric arc furnace just refines+refining of AOD stove ", when the AOD stove is smelted, by being blown into time, the flow control of the nitrogen (or containing nitrogen mixture gas) in the molten steel, realization is produced the steel ingot of the duplex stainless steel of conformance with standard requirement to the control of the N content in the molten steel, improves and smelts qualification rate, reduce production costs, satisfy customer requirements and market demand.
A kind of smelting production method that contains the N duplex stainless steel provided by the invention is characterized in that adopting the mode of " electric arc furnace just refines+refining of AOD stove ", at first in ordinary arc furnace, furnace charge is melted refining just; Then at the AOD stove to liquid steel refining, smelt the qualified duplex stainless steel molten steel of composition and purity, at last high-temperature molten steel is poured into static ingot or continuous casting steel billet:
At first in ordinary arc furnace, furnace charges such as returns, alloy, auxiliary material are melted refining just:
When 1) smelting required starting material such as returns, alloy and auxiliary material batching, starting material carbon content unrestricted (because of AOD has good decarburization effect) is used high carbon alloy (low C Chrome metal powder cost is much higher than high C Chrome metal powder) as far as possible, reduces smelting cost;
2) fusing refining just is by general stainless steel Returning blowing keto technique operation;
3) upper limit among Composition Control: Cr, the Mo is limit among the Ni, Si≤0.30%;
4) draw slag whole before the tapping, guarantee slag free tapping;
5) (tapping temperature is low excessively, can not guarantee that AOD opens blowing temp 〉=1540 ℃ for tapping temperature: T 〉=1620 ℃.)；
In the AOD stove, carry out the melting of duplex stainless steel molten steel then; At carbon period, by adjusting the dividing potential drop of oxygen in nitrogen, oxygen gas mixture, realize the condition of carbon preferential oxidation in the high chromium steel liquid on the one hand, realize increasing in the molten steel purpose of N on the other hand; At reduction period, stir and force deoxidation by intensive rare gas element (nitrogen, argon gas), clean molten steel on the one hand, deoxidation is also removed obnoxious flavour, detrimental impurity in the molten steel, quicken the reduction of chromic oxide in the slag, electric furnace is freed from the heavy burden of high chromium steel liquid decarburization, pass through the switching of nitrogen, argon gas in the rare gas element on the other hand, realize the fine setting of nitrogen content in the molten steel, the bound scope of control N content is within 0.05% (500ppm just):
1) AOD opens blowing temp 〉=1540 ℃ (AOD opens blowing temp when low, is blown into the oxygen in the molten steel, with the chromium reaction, generates chromic oxide, and chromium decreases to be increased, the decarburization difficulty.)；
2) convert the complete slag part, thermometric, sampling analysis (1) of drawing of steel; And according to [Si] content adding lime in the molten steel, lime adding amount=(3.5～4.2) * G * [Si], G are steel-making molten steel in the stove weight; Press the decarburization capacity coefficient, adjust the dividing potential drop of oxygen in nitrogen, oxygen gas mixture and (, in nitrogen, oxygen gas mixture,, adjust the branch drops of oxygen along with the decline of carbon content according to the decarburization capacity coefficient.), being blown into proportionlity in stove is O
2: N
2=(3.0～4.5): 1 nitrogen, oxygen gas mixture, carry out decarburization at the AOD stove, increase N, hyperthermic treatment; Adjust composition according to analysis (1) result and to internal control, limit (Cr reclaims by 95% calculating, and Ni, Mo recovery is pressed 100% and calculated);
3) thermometric, sampling analysis (2) when C is about 0.10% (calculating according to oxygen blast carbon drop formula), and switch nitrogen, oxygen gas mixture flow proportional, proportionlity is O
2: N
2=(1.5～2.5): 1; Thermometric, sampling analysis (3) when C is about 0.05% (calculating according to oxygen blast carbon drop formula), and switch nitrogen, oxygen gas mixture flow proportional, proportionlity is O
2: N
2=(0.3～0.6): 1;
4) when C＜0.010%, stop nitrogen flushing, oxygen gas mixture, change blown inert gas (nitrogen, argon gas) and clean molten steel, deoxidation is also removed obnoxious flavour, detrimental impurity in the molten steel, and inert gas flow is 400～600m
3/ h, the N content of sampling analysis reach on the composition and prescribe a time limit, all Argons; In stove, add the prereduction slag charge, the slag charge proportioning: the lime of (3.7～4.5) * G * [Si], 15～35Kg Si-Fe/ ton steel are (according to original molten steel composition and oxygen blast total, utilize Si oxidisability under the high temperature to be better than the characteristics of Cr, already oxidised chromium is restored, makes total chromium recovery ratio reach 95～97%), electrolytic manganese is an amount of, Al is an amount of; Prereduction time 5～8min, sampling total analysis (4), (5), and draw slag whole;
5) add the reduction slag charge, the slag charge proportioning: 15～25Kg lime/ton steel, 0.6～1.0Kg fluorite/ton steel (that is to say, add with 3～5% of lime adding amount; Be used to improve the flowability of molten steel), Al is an amount of, good for guaranteeing reduction, it is an amount of to add Si-Ca; Nitrogen flushing refining and nitrogen pick-up (the N content in the molten steel has loss at prereduction, reduction period) are so according to N content results and the nitrogen flow of analyzing (4), (5), nitrogen increased amount calculates by 100% rate of recovery;
6) thermometric, sampling analysis (6), according to analyzing (6) fine setting composition, ar blowing refining is also regulated nitrogen in steel content, argon flow amount 400～600m
3/ h (calculating the time that Argon is regulated nitrogen content) according to result who analyzes (6) and denitride amount formula;
7) tapping has B content (improving the high temperature working strength of steel) to require, and banishs with steel during tapping; At last high-temperature molten steel is poured into static ingot or continuous casting steel billet.
The present invention has following advantage:
1. can use cheap high carbon alloy, reduce production costs.
2. smelting operation is simple, and Ultralow Carbon Stainless Steel is operated routinely.
3.AOD divide the decarburization of three phases in the stove, carbon be controlled at below 0.010%.
4. the sulfide of steel, oxide compound, silicate, point-like non-metallic inclusion rank are low, high purity.
5. nitrogen content control accuracy height, cost is low.
Specific embodiments
Certain Iron And Steel Company's steelshop is implemented patent of the present invention, produces duplex stainless steel (C＜0.03%, Cr=22～23% of the 22 stove SAF2205 trades mark, Ni=4.5～6.5%, N=0.15～0.20%, Si＜1%, Mn=0.40～0.80%, P≤0.025%, S≤0.008%, Mo=3.0～3.5%, B=0.0001～0.0010%, oxygen level≤0.0040%, Al≤0.025%; Sulfide≤1 grade, oxide compound≤2 grade, point-like inclusion≤1 grade), its technical process be 20 tons of ac arc furnaces fusing-→ 18 tons of AOD meltings of refining just-→ die casting pours into 1.2 tons of steel ingots (argon for protecting pouring).The first step, electric arc furnace fusing refining just: first furnace is identical with other general stainless steel operation, melts clearly and fluxes greater than 80% back oxygen blast; Molten steel temperature adds reductive agent prereduction during greater than 1660 ℃, and the total analysis of taking a sample after the prereduction draws slag whole; Adjust composition, the upper limit among Cr, the Mo, Ni lower limit, Si≤0.30% according to analytical results; Temperature is greater than 1630 ℃ of tappings.In second step, carry out the melting of duplex stainless steel molten steel at the AOD stove: (1) AOD opens blowing temp 〉=1540 ℃; (2) convert the complete slag part, thermometric T=1568 ℃, sampling analysis (a) of drawing of steel; Add lime (3.5～4.2) * G * [Si]=400Kg; In stove, be blown into nitrogen, (proportionlity is O2 to oxygen gas mixture: N2=(3.0～4.5): 1=4: 1), carry out decarburization, hyperthermic treatment at the AOD stove; Adjust composition according to analysis (a) result and to internal control, limit (Cr reclaims by 96% calculating, and the Ni recovery is pressed 100% and calculated); (3) thermometric T＞1700 ℃, sampling analysis (b) when C is about 0.10% (calculating according to oxygen blast carbon drop formula), and switch nitrogen, oxygen gas mixture flow (O2: N2=(1.5～2.5): 1=2: 1); (4) thermometric, sampling analysis (c) when C is about 0.05%, and switch nitrogen, oxygen gas mixture flow proportional, proportionlity is O2: N2=(0.3～0.6): 1=1: 2; (4) continue the oxygen blast carbon drop, when about 0.010% left and right sides of C, stop nitrogen flushing, oxygen gas mixture, changing blown inert gas (nitrogen, argon gas) cleans molten steel (deoxidation is also removed obnoxious flavour, detrimental impurity in the molten steel,), this moment, the N content of sampling analysis reached the composition upper limit (N=0.20%), and rare gas element all is an argon gas, and argon flow amount is 480m3/h; Add the prereduction slag charge in stove, the slag charge proportioning: (3.5～4.2) * G * [Si]=600Kg lime, 430Kg Si-Fe (22Kg/ ton steel), electrolytic manganese are an amount of.Behind the prereduction time 7min, sampling total analysis (d, e) draws slag whole; (5) add the reduction slag charge, guarantee that reduction is good, Al is an amount of, and it is an amount of to add Si-Ca; Slag charge proportioning: 300Kg lime, (3～5%) * 300Kg=15Kg fluorite; Nitrogen flushing refining and nitrogen pick-up, according to N content (N=0.12%), the nitrogen flow (480m3/h) of sampling total analysis (d, e), nitrogen increased amount calculates by 100% rate of recovery, nitrogen flushing refining 1-2 minute; (6) thermometric, sampling analysis (f), according to analyzing (f) fine setting composition, ar blowing refining 1-2 minute, argon flow amount was 480m3/h; (7) tap, banish 0.0004%～0.0010% B with steel.In the 3rd step, adopt die casting process that high-temperature molten steel is cast into 1.2 tons of steel ingots: to adopt argon for protecting pouring technology (improve molten steel clarity); Teeming temperature is 1525～1535 ℃, the calm 6 minutes time; With rational pouring speed (the 7min duration of pouring), even fusing of covering slag and molten steel are evenly risen, high-temperature molten steel is cast into steel ingot.It is simple that patent of the present invention has smelting operation, the restriction of starting material alloying ingredient is few, it is good that metallurgical power is learned condition, production cost is low, the characteristics of equipment and technology highly versatile, implement the SAF2205 duplex stainless steel that patent of the present invention is produced, its chemical ingredients satisfies internally controlling requirement fully, sulphur in the steel, oxygen, hydrogen richness is near the level of vacuum decarburization method, sulfide, oxide compound, silicate, point-like non-metallic inclusion rank is low, the control accuracy height of nitrogen, the finished product of behind rolling and poling, making, performance meets the user quality standard, qualification rate 100% has satisfied the requirement that domestic scale operation contains the N duplex stainless steel.
Claims (1)
1, the smelting production method that contains the N duplex stainless steel is characterized in that adopting the mode of " electric arc furnace just refines+refining of AOD stove ", at first in ordinary arc furnace, furnace charge is melted refining just; Then at the AOD stove to liquid steel refining, smelt the qualified duplex stainless steel molten steel of composition and purity, at last high-temperature molten steel is poured into static ingot or continuous casting steel billet:
The first step, in ordinary arc furnace, melt refining just to furnace charges such as returns, alloy, auxiliary materials:
When 1) smelting required starting material such as returns, alloy and auxiliary material batching, the starting material carbon content is unrestricted, uses high carbon alloy as far as possible;
2) fusing refining just is by general stainless steel Returning blowing keto technique operation;
3) upper limit among Composition Control: Cr, the Mo is limit among the Ni, Si≤0.30%;
4) draw slag whole before the tapping, guarantee slag free tapping;
5) tapping temperature: T 〉=1620 ℃;
In second step, in the AOD stove, carry out the melting of duplex stainless steel molten steel; At carbon period, by adjusting the dividing potential drop of oxygen in nitrogen, oxygen gas mixture, realize the condition of carbon preferential oxidation in the high chromium steel liquid on the one hand, realize increasing in the molten steel purpose of N on the other hand; At reduction period, stir and force deoxidation by intensive rare gas element (nitrogen, argon gas), quicken the reduction of chromic oxide in the slag on the one hand, electric furnace is freed from the heavy burden of high chromium steel liquid decarburization, pass through the switching of nitrogen, argon gas in the rare gas element on the other hand, realize the fine setting of nitrogen content in the molten steel, the bound scope of control N content is within 0.05%:
1) AOD opens blowing temp 〉=1540 ℃;
2) convert the complete slag part, thermometric, sampling analysis (1) of drawing of steel; And according to [Si] content adding lime in the molten steel, lime adding amount=(3.5～4.2) * G * [Si], G are steel-making molten steel in the stove weight; Being blown into proportionlity in stove is O
2: N
2=(3.0～4.5): 1 nitrogen, oxygen gas mixture, carry out decarburization at the AOD stove, increase N, hyperthermic treatment; Adjusting composition according to analysis (1) result limits to internal control: Cr reclaims by 95% calculating, and Ni, Mo recovery is pressed 100% and calculated;
3) thermometric, sampling analysis (2) when C is about 0.10%, and switch nitrogen, the oxygen gas mixture flow proportional is O
2: N
2=(1.5～2.5): 1; Thermometric, sampling analysis (3) when C is about 0.05%, and switch nitrogen, the oxygen gas mixture flow proportional is O
2: N
2=(0.3～0.6): 1;
4) when C＜0.010%, blow off nitrogen, oxygen gas mixture change blown inert gas (nitrogen, argon gas) and clean molten steel, and deoxidation is also removed obnoxious flavour, detrimental impurity in the molten steel, and inert gas flow is 400～600m
3/ h, the N content of sampling analysis reach on the composition and prescribe a time limit, all Argons; Add the prereduction slag charge in stove, the slag charge proportioning: the lime of (3.7～4.5) * G * [Si], 15～35KgSi-Fe/ ton steel, electrolytic manganese is an amount of, Al is an amount of; Prereduction time 5～8min, sampling total analysis (4), (5), and draw slag whole;
5) add the reduction slag charge, the slag charge proportioning: 15～25Kg lime/ton steel, 0.6～1.0Kg fluorite/ton steel, Al are an amount of, and Si-Ca is an amount of; Nitrogen flushing refining and nitrogen pick-up, according to N content results and the nitrogen flow of analyzing (4), (5), nitrogen increased amount calculates by 100% rate of recovery;
6) thermometric, sampling analysis (6), according to analyzing (6) fine setting composition, ar blowing refining is also regulated nitrogen in steel content, argon flow amount 400～600m
3/ h calculates the time that Argon is regulated nitrogen content according to result who analyzes (6) and denitride amount formula;
7) tapping has the B content requirement, banishs with steel during tapping;
At last high-temperature molten steel is poured into static ingot or continuous casting steel billet.
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