CN107955857B - A kind of control nitrogen method during AOD smelting stainless steel - Google Patents
A kind of control nitrogen method during AOD smelting stainless steel Download PDFInfo
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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
- C21C5/005—Manufacture of stainless steel
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/068—Decarburising
- C21C7/0685—Decarburising of stainless steel
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract
The invention discloses a kind of control nitrogen methods during AOD smelting stainless steel, the AOD smelting stainless steel process includes decarburizing phase and reduction phase, the decarburizing phase, the nitrogen content in the molten steel of decarburization end be chromium, manganese, molybdenum mass percentage summation 1/100-1/75；The reduction phase adjusts the nitrogen content in molten steel to target value according to finished steel nitrogen content, and increasing method for nitrogen is gas nitrogen alloying and/or solid nitrogen alloying, and denitrification method is blowing argon gas.The present invention accomplishes the hit at first time of nitrogen according to the specific requirement of different steel grade nitrogen contents；Stablize smelting cycle；According to the additional amount of the GN 2 alloying time and solid nitrogen, determination process temperature is precisely controlled；Prevent to cause the fluctuations of properties of product because nitrogen hit rate is lower.
Description
Technical field
The invention belongs to metallurgical technology fields, and in particular to a kind of control nitrogen method during AOD smelting stainless steel.
Background technique
Current China steel and iron industry is in the product restructuring stage, and special steel ratio is gradually increased, and stainless steel, no magnetic
Steel, corrosion-resisting steel, creep resistant, anti-fatigue steel, heat resisting steel etc. are the fine work in special steel again.With China's Aviation Industry and ocean development
The application of fast development, these special materials is increasingly brought into schedule.
Nitrogen has forms and stablizes austenite effect strongly, reduces martensite transformation temperature Ms and Md30, is development without magnetic
The ideal material of steel.
Nitrogen decomposing shape ammonification or ammonium ion in corrosive liquid reduce the acidity of corrosive liquid, and then improve passivation effect.Simultaneously
The presence of nitrogen additionally aids to form fine and close nitrogen, protective oxide film.Nitrogen can be to corrode member in equilibrium assignmen complex phase or multinomial steel
Element exists, and avoids generating serious selective corrosion.It is thus the ideal material for developing corrosion-resisting steel, Yu Haiyang is widely applied and opens
Hair, petrochemical field.
Nitrogen at low temperature, can significantly improve free electronic concentration in austenite structure, and the shortrange order of atom is promoted to arrange
Column, are conducive to be combined between atom with metallic bond, improve the toughness of material；Simultaneously because the presence of nitrogen, leads to austenite lattice
Expansion, and then improve austenite material yield strength.And in the deformation process of material, since nitrogen is to reduce stacking fault energy
Element, promote material crystal defect fault, twin structure are generated in deformation process, generated when deflection is larger a certain amount of
Martensite.Nitrogenous austenitic stainless steel is a kind of obdurability material.
Application of the nitrogen in high-temerature creep, tired material.It is mainly analyzed in terms of two, first inside solid solution, due to nitrogen
Presence, sliding deformation is mainly based on planar slip, in high frequency short arc range, since planar slip has invertibity, because
And micro-crack is not likely to produce inside solid solution.Consider from grain boundaries, since the affinity of nitrogen and chromium, molybdenum is better than carbon and chromium, molybdenum
Affinity, thus nitrogen can promote chromium, molybdenum evenly distributing in matrix, refine grain boundary carbide particle, inhibit gold
The precipitation of phase between category, avoids the generation of crystal boundary micropore；The presence of nitrogen simultaneously, austenite are dissolved body tissue medium or short range ordered arrangement,
Make Austenite Grain Refinement, mitigate the aggregation extent of dislocation on crystal boundary, reduce boundary stress, avoid crystal boundary generate serious sliding and
Form crystal boundary micro-crack.Which thereby enhance the creep resistant fracture property of material.It is the ideal material for developing aircraft industry
The application of low-carbon, high nitrogen, nickeliferous, manganese, cobalt martensitic material so that in a corrosive environment high-strength material be able to it is fast
Speed development.Since the phosphorus content of the material is lower, corrosion resistance is higher；There is martensitic structure under conditions of use simultaneously,
Thus intensity is apparently higher than nitrogenous austenitic stainless steel.
Nitrogen can effectively adjust austenite and ferritic ratio in dual phase steel, thus be in two phase stainless steel can not or
Scarce element.Nitrogen be also section nickel element, the ability for forming austenite is 20-30 times of nickel, can be effectively reduced material at
This.
But in the method for control nitrogen, unified control nitrogen theory is not formed in industry so far.For these reasons, develop
Nitrogenous steel has and its important strategic importance.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of control nitrogen methods during AOD smelting stainless steel.
Taken technical solution is as follows in order to solve the above problem by the present invention: the control nitrogen during a kind of AOD smelting stainless steel
Method, the AOD smelting stainless steel process include decarburizing phase and reduction phase, the decarburizing phase, in the molten steel of decarburization end
Nitrogen content be chromium, manganese, molybdenum mass percentage summation 1/100-1/75；The reduction phase is adjusted according to finished steel nitrogen content
For nitrogen content in whole molten steel to target value, increasing method for nitrogen is gas nitrogen alloying and/or solid nitrogen alloying, and denitrification method is to blow
Argon gas.
Reduction phase of the present invention, when chromium+manganese+molybdenum content in molten steel≤30%, when finished steel nitrogen content≤3000ppm,
Using gas nitrogen alloying；When finished steel nitrogen content > 3000ppm, carry out in two stages, nitrogen content in the 0-3000ppm stage,
Using gas nitrogen alloying, nitrogen content is more than the 3000ppm stage, and using solid nitrogen alloying, chromium nitride or nitrogen is can be selected in alloy
Change manganese.
Reduction phase of the present invention, in molten steel when chromium+manganese+molybdenum content > 30%, when finished steel nitrogen content≤3500ppm,
Using gas nitrogen alloying；When finished steel nitrogen content > 3500ppm, carry out in two stages, nitrogen content in the 0-3500ppm stage,
Using gas nitrogen alloying, nitrogen content is more than the 3500ppm stage, using solid nitrogen alloying.
The relationship of reduction phase of the present invention, the GN 2 alloying step, the absorptivity of nitrogen and finished steel nitrogen content is such as
Under: 1m3 nitrogen is under the conditions of different taps, nitrogen pick-up total amount Q=L/W*1000000, and wherein Q:1m3 nitrogen is different nitrogenous
Nitrogen pick-up total amount in the molten steel in section, unit ppm；W: Metal Weight, units/kg；Nitrogen pick-up of the L:1m3 nitrogen in different nitrogenous sections
Amount, units/kg.
Reduction phase described in invention, the GN 2 alloying step, blowing argon gas go nitrogen quantity to contain with finished steel nitrogen
Amount is as follows: under the conditions of different taps, denitrification total amount G=K/W*1000000, wherein G:1m3 argon gas exists 1m3 argon gas
Different nitrogenous section denitrogenation total amounts, unit ppm；W: Metal Weight, units/kg；Denitrogenation of the L:1m3 argon gas in different nitrogenous sections
Amount, units/kg.
The relationship of reduction phase of the present invention, solid nitrogen alloying step, the absorptivity of nitrogen and finished steel nitrogen content is such as
Under: in solid nitrogen alloying, the absorptivity of nitrogen changes less substantially, is calculated generally according to 50-60%.
1m3 nitrogen different nitrogenous section nitrogen increased amount reference tables 1 in molten steel, the different nitrogenous sections of 1m3 argon gas go nitrogen quantity to join
Examine table 2.
The different nitrogenous section nitrogen increased amounts of 1 1m3 nitrogen of table
Nitrogen quantity is gone in the different nitrogenous sections of 2 1m3 argon gas of table
The relationship of reduction phase of the present invention, solid nitrogen alloying step, the absorptivity of nitrogen and finished steel nitrogen content is such as
Under: in solid nitrogen alloying, the absorptivity of nitrogen changes less substantially, is calculated generally according to 50-60%.
Decarburizing phase of the present invention, when liquid steel temperature is 1600 DEG C, the nitrogen content in the molten steel of decarburization end is chromium, manganese, molybdenum
The 1/75 of mass percentage summation.
Decarburizing phase of the present invention, when liquid steel temperature is 1700 DEG C, the nitrogen content in the molten steel of decarburization end is chromium, manganese, molybdenum
The 1/100 of mass percentage summation.
AOD smelting stainless steel of the present invention, including the soft geneva of nitrogen austenitic stainless steel, two phase stainless steel, low-carbon high-nitrogen
Body stainless steel.
The present invention is according to the requirement of finished product nitrogen content, it is first determined the GN 2 alloying time temperature drop and solid nitrogen alloy add
Enter the temperature drop of amount, and then obtain temperature after decarburization end temperature or manganese addition heating with heat Balance Calculation, in favor of smelting process
Temperature control and finishing slag quality guarantee, avoid because temperature control it is improper caused by secondary oxidation of steel due to deteriorate steel.
The beneficial effects of adopting the technical scheme are that the 1, present invention is according to the specific of different steel grade nitrogen contents
It is required that accomplishing the hit at first time of nitrogen；Stablize smelting cycle；According to the additional amount of the GN 2 alloying time and solid nitrogen, determine
Process temperature is precisely controlled；Prevent to cause the fluctuations of properties of product because nitrogen hit rate is lower.2, the present invention specifies that nitrogen closes
Aurification time, and then accurately controlled the temperature after nitrogen alloying, avoid temperature it is relatively low when cause secondary oxygen supply, deteriorate steel
Matter, when temperature drift, cause secondary alloyed, the problems such as increasing gas, auxiliary material, refractory consumption.
Specific embodiment
Embodiment 1
By taking high-nitrogen austenitic stainless steel 0Cr25Ni16Mn6NV steel grade as an example, illustrate its control nitrogen process, 60 tons of tap.
This steel grade main chemical compositions and mass percentage are as follows: C:0.04-0.05%, Cr:25-26%, Ni:15.5-
16.5%, Mn:5.5-6.5%, N:0.40-0.50%.
Cr+Mn+Mo content is 31%, decarbonizing process whole process nitrogen flushing, 1700 DEG C of decarburization latter stage temperature, nitrogen in the molten steel of decarburization end
Content is 0.31%.During reduction period gas nitrogen alloying, calculated according to nitrogen pick-up formula, nitrogen content is increased to by 3100ppm
3250ppm needs nitrogen pick-up 150ppm, this range 1m3 N Gas Alloying value 0.12/60000*1000000=2ppm needs nitrogen blowing 150/
2=75m³；Nitrogen content increases to 3500ppm by 3250ppm, needs nitrogen pick-up 250ppm, this range 1m3 N Gas Alloying value 0.06/
60000*1000000=1ppm needs 250/1=250m3 of nitrogen blowing；It is total to be blown into nitrogen 75+250=325m3；Nitrogen content is about at this time
3500ppm.During reduction period solid nitrogen alloying, 1200 kilograms of chromium nitride are added, nitrogen recovery 60%, chromium nitride is nitrogenous
8.30%, nitrogen content is increased into about 4500ppm.Actually detected value 4350ppm.
Embodiment 2
By taking duplex stainless steel 2205 steel grade as an example, Chinese Industrial Standards (CIS) 00Cr22Ni5Mo3N illustrates that it controls nitrogen process, tap
30 tons.
This steel grade main chemical compositions and mass percentage are as follows: C≤0.03%, Cr:21.5-22.5%, Ni:5.0-
5.5%, Mn:1.0%, Mo:3.0%, N:0.22%.
Cr+Mn+Mo content is 26%, carbon period whole process nitrogen flushing, 1680 DEG C of decarburization latter stage temperature, nitrogen content about 0.26%,
Higher than product nitrogen requirement.During reduction period gas nitrogen alloying, calculated according to nitrogen pick-up, denitrogenation formula.
Nitrogen content, which increases to 2750ppm by 2600ppm, needs nitrogen pick-up 150ppm, this nitrogenous section 1m3 N Gas Alloying value 0.24/
30000*1000000=8ppm needs 150/8=18.75m3 of nitrogen blowing；Nitrogen content increases to 2900ppm by 2750ppm, needs nitrogen pick-up
150ppm, this nitrogenous section 1m3 nitrogen pick-up value 0.18/30000*1000000=6ppm, needs 150/6=25m3 of nitrogen blowing.
Nitrogen content is down to 2750ppm by 2900ppm, need to drop nitrogen 150ppm, this nitrogenous section 1m3 argon gas denitrogenation value 0.60/
30000*1000000=20ppm needs 150/20=7.5m3 of blowing argon gas；Nitrogen content is down to 2500ppm by 2750ppm, need to drop nitrogen
250ppm, this nitrogenous section 1m3 argon gas denitrogenation value 0.54/30000*1000000=18ppm, needs 250/18=14m3 of blowing argon gas；Nitrogen
Content is down to 2250ppm by 2500ppm, need to drop nitrogen 250ppm, this nitrogenous section 1m3 argon gas denitrogenation value 0.48/30000*
1000000=16ppm needs 250/16=16m3 of blowing argon gas.Total nitrogen blowing 44m3, argon gas 37m3 altogether.Nitrogen can be controlled about
2250ppm.Actually detected value 2200ppm
This steel grade is first blown into nitrogen, after be blown into argon gas purpose mainly guarantee certain air-blowing quantity, meet the recovery time
It needs, the general recovery time cannot be below 5 minutes.
Embodiment 3
By taking martensitic stain less steel 1Cr12NiMoN as an example, illustrate its control nitrogen process, 90 tons of tap.
This steel grade main chemical compositions and mass percentage are as follows: C:0.10-0.15%, Cr:12-14%, Ni:1.0-
1.5%, Mo:1.8-2.5%, N:0.10-0.12%.
Cr+Mn+Mo content is about 14%, carbon period whole process nitrogen flushing, 1620 DEG C of decarburization end temperature, and decarburization end nitrogen content about exists
0.16%；During reduction period gas nitrogen alloying, calculated according to nitrogen pick-up, denitrogenation formula, nitrogen content is increased to by 1600ppm
1750ppm needs nitrogen pick-up 150ppm, this nitrogenous section 1m3 N Gas Alloying value 0.48/90000*1000000=5.33ppm needs nitrogen flushing
150/5.33=28m3 of gas；Nitrogen content increases to 2000ppm by 1750ppm, needs nitrogen pick-up 250ppm, this nitrogenous section 1m3 nitrogen pick-up value
0.42/90000*1000000=4.67ppm needs 250/4.67=53m3 of nitrogen blowing.
Nitrogen content is down to 1750ppm by 2000ppm, need to drop nitrogen 250ppm, this nitrogenous section 1m3 argon gas denitrogenation value 0.36/
90000*1000000=4ppm needs 250/4=62.5m3 of blowing argon gas；Nitrogen content is down to 1500ppm by 1750ppm, need to drop nitrogen
250ppm, this nitrogenous section 1m3 argon gas denitrogenation value 0.30/90000*1000000=3.33ppm, needs 250/3.33=75m of blowing argon gas
³；Nitrogen content is down to 1250ppm by 1500ppm, need to drop nitrogen 250ppm, this nitrogenous section 1m3 argon gas denitrogenation value 0.24/90000*
1000000=2.67ppm needs 250/2.67=93m3 of blowing argon gas；Nitrogen content is down to 1100ppm by 1250ppm, need to drop nitrogen
150ppm, this nitrogenous section 1m3 argon gas denitrogenation value 0.18/90000*1000000=2.00ppm, needs 150/2=75m3 of blowing argon gas.
Total nitrogen blowing 80m3, argon gas argon gas 305m3 altogether.Nitrogen can be controlled in about 1100ppm, actually detected value 1000ppm.
This steel grade is first blown into nitrogen, after be blown into argon gas purpose mainly guarantee certain air-blowing quantity, meet the recovery time
It needs, the general recovery time cannot be below 5 minutes.
The above embodiments are only used to illustrate and not limit the technical solutions of the present invention, although referring to above-described embodiment to this hair
It is bright to be described in detail, those skilled in the art should understand that: still the present invention can be modified or be waited
With replacement, without departing from the spirit or scope of the invention, or any substitutions, should all cover in power of the invention
In sharp claimed range.
Claims (8)
1. a kind of control nitrogen method during AOD smelting stainless steel, which is characterized in that the AOD smelting stainless steel process includes
Decarburizing phase and reduction phase, the decarburizing phase, the nitrogen content in the molten steel of decarburization end are that chromium, manganese, molybdenum mass percentage are total
The 1/100-1/75 of sum；The reduction phase adjusts nitrogen content in molten steel to target value, nitrogen pick-up according to finished steel nitrogen content
Method is gas nitrogen alloying and/or solid nitrogen alloying, and denitrification method is blowing argon gas, the reduction phase, chromium+manganese in molten steel
When+molybdenum content≤30%, when finished steel nitrogen content≤3000ppm, using gas nitrogen alloying；Finished steel nitrogen content > 3000ppm
When, it carrying out in two stages, nitrogen content is in the 0-3000ppm stage, and using gas nitrogen alloying, nitrogen content is more than the 3000ppm stage,
Using solid nitrogen alloying.
2. a kind of control nitrogen method during AOD smelting stainless steel, which is characterized in that the AOD smelting stainless steel process includes
Decarburizing phase and reduction phase, the decarburizing phase, the nitrogen content in the molten steel of decarburization end are that chromium, manganese, molybdenum mass percentage are total
The 1/100-1/75 of sum；The reduction phase adjusts nitrogen content in molten steel to target value, nitrogen pick-up according to finished steel nitrogen content
Method is gas nitrogen alloying and/or solid nitrogen alloying, and denitrification method is blowing argon gas, the reduction phase, chromium+manganese in molten steel
When+molybdenum content > 30%, when finished steel nitrogen content≤3500ppm, using gas nitrogen alloying；Finished steel nitrogen content > 3500ppm
When, it carrying out in two stages, nitrogen content is in the 0-3500ppm stage, and using gas nitrogen alloying, nitrogen content is more than the 3500ppm stage,
Using solid nitrogen alloying.
3. the control nitrogen method during a kind of AOD smelting stainless steel according to claim 1 or 2, which is characterized in that described
Reduction phase, the GN 2 alloying step, the absorptivity of nitrogen and the relationship of finished steel nitrogen content are as follows: 1m3 nitrogen goes out in difference
Under the conditions of steel amount, nitrogen pick-up total amount Q=L/W*1000000, wherein the nitrogen pick-up in the molten steel in different nitrogenous sections of Q:1m3 nitrogen is total
Amount, unit ppm；W: Metal Weight, units/kg；Nitrogen increased amount of the L:1m3 nitrogen in different nitrogenous sections, units/kg.
4. the control nitrogen method during a kind of AOD smelting stainless steel according to claim 1 or 2, which is characterized in that described
Reduction phase, the GN 2 alloying step, blowing argon gas remove nitrogen quantity and finished steel nitrogen content is as follows: 1m3 argon gas is in difference
Under the conditions of tap, denitrification total amount G=K/W*1000000, wherein G:1m3 argon gas is in different nitrogenous section denitrogenation total amounts, unit
ppm；W: Metal Weight, units/kg；Denitrogenation amount of the L:1m3 argon gas in different nitrogenous sections, units/kg.
5. the control nitrogen method during a kind of AOD smelting stainless steel according to claim 1 or 2, which is characterized in that described
Reduction phase, solid nitrogen alloying step, the absorptivity of nitrogen and the relationship of finished steel nitrogen content are as follows: in solid nitrogen alloying
When, the absorptivity of nitrogen is calculated according to 50-60%.
6. the control nitrogen method during a kind of AOD smelting stainless steel according to claim 1 or 2, which is characterized in that described
Decarburizing phase, when liquid steel temperature is 1600 DEG C, the nitrogen content in the molten steel of decarburization end is chromium, manganese, molybdenum mass percentage summation
1/75。
7. the control nitrogen method during a kind of AOD smelting stainless steel according to claim 1 or 2, which is characterized in that described
Decarburizing phase, when liquid steel temperature is 1700 DEG C, the nitrogen content in the molten steel of decarburization end is chromium, manganese, molybdenum mass percentage summation
1/100。
8. the control nitrogen method during a kind of AOD smelting stainless steel according to claim 1 or 2, which is characterized in that described
AOD smelting stainless steel, including the soft martensitic stain less steel of nitrogen austenitic stainless steel, two phase stainless steel, low-carbon high-nitrogen.
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| JP2010144195A (en) * | 2008-12-16 | 2010-07-01 | Nisshin Steel Co Ltd | Method for manufacturing high nitrogen-containing stainless steel |
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| CN100567512C (en) * | 2007-03-27 | 2009-12-09 | 宝山钢铁股份有限公司 | A kind of nitrogen content control method for smelting stainless steel by vacuum oxygen decarburization device |
| CN101748242B (en) * | 2010-01-14 | 2011-05-25 | 武昌船舶重工有限责任公司 | Method for precisely controlling nitrogen content in extra low carbon stainless steel with nitrogen |
| CN103571999A (en) * | 2012-07-19 | 2014-02-12 | 宝钢不锈钢有限公司 | Method for smelting nitrogen-controlling martensite stainless steel through total molten iron |
| CN107245637B (en) * | 2017-06-26 | 2019-04-12 | 永兴特种不锈钢股份有限公司 | A kind of AOD smelts the method and a kind of AOD furnace of high manganese stainless steel |
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| JP2010144195A (en) * | 2008-12-16 | 2010-07-01 | Nisshin Steel Co Ltd | Method for manufacturing high nitrogen-containing stainless steel |
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