CN101058837A - Smelting method for decarburization and denitrogenation of ultra-pure ferrite stainless steel - Google Patents
Smelting method for decarburization and denitrogenation of ultra-pure ferrite stainless steel Download PDFInfo
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Abstract
The invention discloses a decarburizing and denitrify smelt method of ultrapure ferrite non-corrodible steel, which comprises the following steps: (1) putting the ladle in vacuum jar and evacuating at 260-350mbar air pressure, opening sub-aerator argon gas; (2) decarburizing with oxygen blast when the air pressure in vacuum jar reduces to 200-250mbar; (3) stopping oxygen blast when the carbon content in the liquid steel reduces to 0. 03%-0. 05%, boiling more than 20 minutes when vacuum degree isn't more than 1mbar( air mixing strength in the bottom of ladle >= 13L/(min, t); (4) adding ferrosilicium, deacidizing oxygenized chrome and the other metallic element in the oxygen blast procedure(mixing strength> 10L/(min, t), vacuum degree <= 5mbar); (5)adding aluminum in order to deoxidize(mixing strength> 10L/(min, t), vacuum degree <= 5mbar, deoxidation time is 5-10 minutes); (6) adjusting alloys finely; (7) closing agitation subaeration air; (8) breaking vacuum. The invention provides a simple technology and a short smelt time.
Description
Technical field
The present invention relates to the smelting process of a kind of super-purity ferrite stainless steel decarburization, denitrogenation.
Background technology
There are C, the strong also stable austenite that forms of N interstitial element in the ferritic stainless steel, extremely harmful to ferritic stainless steel, mainly be because C, the velocity of diffusion of N element in ferritic stainless steel are fast, be about 600 times in austenite, have carbon in the process of cooling after heat, nitrides precipitate is separated out, caused 475 ℃ of fragility of ferritic stainless steel, high-temperature brittleness, room temperature toughness is low, brittle transition temperature is high, to shortcomings such as breach sensitivities.Therefore, the metallargist is devoted for years to carbon, the nitrogen content in reducing ferritic stainless steel, thereby overcomes the above-mentioned deficiency of ferritic stainless steel.
Extremely low C, N content are the notable attribute of super-purity ferrite stainless steel, and depth decarburization, denitrogenation also become the core technology that super-purity ferrite stainless steel is smelted.It is negative to the interaction of the carbon in the steel, nitrogen that super-purity ferrite stainless steel all contains element such as a large amount of chromium, molybdenum and molybdenum element, consider from thermodynamics, this class steel carbon, nitrogen content be reduced to one low-level than other steel grade difficulty more.
Before last century the seventies, the difficulty that electric furnace process is smelted super-purity ferrite stainless steel is very big, in the seventies later stage in last century, begins to develop this class steel both at home and abroad.After decompression decarburization, denitrogenation and dilution decarburization, denitrogenation occurred, super-purity ferrite stainless steel had obtained bigger development.External advanced iron and steel enterprise compares early the research of super-purity ferrite stainless steel, and equipment and technology are comparatively advanced, adopts VOD-PB and SS-VOD method to produce super-purity ferrite stainless steel usually.The VOD-PB method is to blow powdery refining agent (as powdered iron ore etc.) to weld pool surface under vacuum condition, pulvis promotes decarburization, denitrification reaction to carry out after entering the molten bath, though decarburization, the denitrification effect of this method are very good, its technology and equipment complexity, cost are also high.The SS-VOD method is to be blown into a large amount of Ar gas from a plurality of porous plugs of ladle bottom, and the violent stirring molten bath smelts ultrapure stainless steel, and the splash of this method in smelting process is serious, argon gas consumption is big.China since last century the eighties develop this class stainless steel, the main equipment of " vacuum induction furnace+electron beam remelting stove " and the method for adopting smelted, " a kind of top-bottom reblowing vacuum inductive stove " as publication number CN170366A, and CN1514033A " a kind of vacuum induction melting method of super-purity ferrite stainless steel ", these smelting processes need expensive high pure raw material, and decarburization, denitrogenation time length and output are little.The report that at present China's scale production super-purity ferrite stainless steel method still is in conceptual phase, particularly carbon drop, success is not also seen in the exploitation of falling nitrogen technology.
Summary of the invention
For the above-mentioned deficiency of the method that overcomes existing ferritic stainless steel decarburization, denitrogenation, the invention provides and a kind ofly smelt decarburization, the denitrogenation method of super-purity ferrite stainless steel with the VOD stove, this decarburization, denitrification process is simple, tap to tap time is short.
The present invention smelts the method that super-purity ferrite stainless steel reduces carbon, reduces nitrogen with the VOD stove, and major equipment has ladle, vacuum tank, oxygen blowing device, feed pot and vacuum system.
One, equipment requirements
(1) system load (being vacuum tank) final vacuum≤1mbar;
(2) the maximum stirring intensity 〉=13L/ (min.t) of ladle bottom gas.
Two, the initial technical qualification requirement of VOD
(1) molten steel initial temperature T 〉=1600 ℃;
(2) initial [Si]≤0.20% of molten steel;
(3) initial 0.40%≤[C]≤0.70% of molten steel
(4) initial thickness of slag layer d≤50mm;
(5) initial [the N]≤200ppm of molten steel;
(6) ladle freeboard H 〉=1300mm can adjust H according to different equipment.
Three, this ferritic stainless steel reduces carbon, the method that reduces nitrogen comprises following step successively:
(1) VOD will be housed handle before the ladle of molten steel to put into vacuum tank airtight, vacuumized 3 minutes, the interior air pressure of vacuum tank remains on 260-350mbar, is generally 300mbar, opens BOTTOM ARGON BLOWING gas;
(2) when reducing to 200-250mbar, the air pressure in the vacuum tank begins oxygen decarburization, oxygen decarburization is divided into six stages, and each oxygen decarburization stage is controlled corresponding oxygen blast flow, blowing oxygen quantity (by decarburization model control), oxygen rifle height, ladle bottom stirring intensity and vacuum tightness;
(3) when the content of carbon in the molten steel is reduced to 0.03%-0.05% (being calculated by decarburization model), stop oxygen blast, carry out the high vacuum boiling, i.e. denitrogenation under decarburization and the high vacuum under high vacuum, when the vacuum tightness in the vacuum tank is not more than 1mbar, boiling time 〉=20 minute; Ladle bottom gas stirring intensity 〉=13L/ (min.t);
(4) add ferrosilicon, chromium and the reduction of other metallic element with the oxidation of oxygen blast stage, ferrosilicon add-on=molten steel terminal point requires silicone content * molten steel weight ÷ ferrosilicon silicon content ÷ ferrosilicon rate of recovery, add lime simultaneously, (lime of adding, the amount of fluorite are fluorite: 7kg/t to the fluorite material, lime: 25kg/t) slag making, 10～15 minutes recovery times, the bottom blowing stirring intensity is greater than 10L/ (min.t), vacuum tightness≤5mbar;
(5) add aluminium deep deoxidation (Al add-on 2.5kg/t), stirring intensity is greater than 10L/ (min.t), vacuum tightness≤5mbar, deaeration time 5～10 minutes;
(6) alloy fine setting, 5～10 minutes even time of composition;
(7) close bottom blowing and stir gas;
(8) treat to open vacuum valve destruction vacuum after the molten steel face calmness;
(9) open vacuum cover, thermometric, sampling, the content that temperature and composition meet C in the enterprise technology requirement molten steel is not more than 0.01%, and the content of N is not more than 100ppm.Pour into a mould then.If C, N content do not meet, can going just, furnace heavily refines; If other composition and temperature are nonconforming, can go other refining furnace adjustment.
VOD of the present invention smelts super-purity ferrite stainless steel decarburization, denitrogenation method, and to liquid steel temperature requirement before handling 〉=1600 ℃, the molten steel initial carbon is 0.40～0.70%; Height, flow, vacuum tightness and the Argon intensity of control oxygen rifle in the oxygen blast process; Oxygen blast finishes back control boiling time, vacuum tightness and Argon intensity, molten steel terminal point C, N content all can be reduced to below the 100ppm.Technology of the present invention is simple, short, short splash tap to tap time is few, argon gas consumes little.
Embodiment
Describe the embodiment of the method for the decarburization of this super-purity ferrite stainless steel, denitrogenation in detail below in conjunction with embodiment, but the embodiment of the method for the decarburization of this super-purity ferrite stainless steel, denitrogenation is not limited to following embodiment.
Embodiment one
The equipment of present embodiment and VOD starting condition require: 75 tons of upper dynamic VOD final vacuum≤1mbar, the maximum stirring intensity 17.2L/ (min.t) of steel ladle bottom argon blowing.The ladle freeboard is the top of the slag to the vertical range H of ladle upper edge is 1350mm, 1649 ℃ of molten steel initial temperatures, and thickness of slag layer is 40mm, and molten steel weight is 72.1 tons, and the smelting steel grade is 00Cr17Mo.
The chemical ingredients (weight) of molten steel was before VOD handled:
C：0.587％ Si：0.1％ Mn：0.09％ P：0.020％
S：0.019％ Cr：17.39％ Mo：1.13％ N(ppm)：158
All the other are iron and unavoidable impurities.
The step of the super-purity ferrite stainless steel decarburization of present embodiment, the method for denitrogenation is as follows:
(1) VOD will be housed handle before the ladle of molten steel to put into vacuum tank airtight, vacuumized 2 minutes, Argon pipe bottom opening, stirring intensity is 2.1L/ (min.t).
(2) begin oxygen decarburization when the indoor air pressure of vacuum is reduced to 205mbar, the level two that oxygen blast flow and oxygen rifle height Danieli Off Mecc provide is controlled automatically.
Six stages of oxygen decarburization, each stage oxygen blast flow, blowing oxygen quantity, oxygen rifle height, ladle bottom Argon intensity are as follows with vacuum tightness: (blowing oxygen quantity in each stage is according to starting condition and different, blowing oxygen quantity is the accumulative total in each stage, each time in stage, oxygen blast was all divided the stage by flow and blowing oxygen quantity decision)
| The oxygen blast stage | Oxygen blast flow Nm 3/h | Oxygen rifle height mm | Ladle argon-blown intensity L/ (min.t) | Vacuum tightness mbar |
| One two three four five six | 1320 1512 1424 1374 1212 1134 | 1615 1524 1524 1455 1455 1411 | 4.8 5.9 5.9 8.2 8.2 11.1 | 205 115 105 75 52 35 |
(3) stop oxygen blast when carbon content in the molten steel is 0.04, this moment, blowing oxygen quantity reached 759Nm
3, the 3 minutes final vacuum degree value of reaching capacity 0.5mbar, boiling is 21 minutes under this vacuum tightness, and ladle bottom Argon intensity is 16L/ (min.t);
(4) add ferrosilicon 350kg, lime 1615kg, fluorite material 420kg, with the chromium and the reduction of other metallic element of the oxidation of oxygen blast stage, the recovery time is 10 minutes, the vacuum tightness in the argon bottom-blowing intensity 16.5L/ (min.t), vacuum tank is 1mbar;
(5) add 180kg aluminium deep deoxidation, bottom blowing argon gas intensity is 15.2L/ (min.t), and the vacuum tightness in the vacuum tank is 3mbar, deaeration time 10 minutes;
(6) close bottom blowing and stir gas;
Molten steel face calmness after (7) 2 minutes is opened vacuum valve and is destroyed vacuum;
(8) open vacuum cover, the temperature of measuring molten steel is 1605 ℃, sampling, and the chemical ingredients (weight) after the decarburization of VOD ferritic stainless steel, the denitrogenation is:
C：0.003％ Si：0.08％ Mn：0.1％ P：0.015％
S：0.0018％ Cr：17.6％ Mo：1.14％ N(ppm)：65
All the other are iron and unavoidable impurities.Meet technical requirements, the cast of coming out of the stove.70 minutes treatment times.
Embodiment two
The equipment of present embodiment and VOD starting condition require: 75 tons of upper dynamic VOD final vacuum≤1mbar, the maximum stirring intensity 16.5L/ (min.t) of steel ladle bottom argon blowing.The ladle freeboard is the top of the slag to the vertical range H of ladle upper edge is 1400mm, 1619 ℃ of molten steel initial temperatures, and thickness of slag layer is 30mm, and molten steel weight is 70.5 tons, and the smelting steel grade is 00Cr18Mo2.
The chemical ingredients (weight) of molten steel was before VOD handled:
C：0.647％ Si：0.15％ Mn：0.20％ P：0.020％
S：0.018％ Cr：18.39％ Mo：2.13％ N(ppm)：184
All the other are iron and unavoidable impurities.
The step of the super-purity ferrite stainless steel decarburization of present embodiment, the method for denitrogenation is as follows:
(1) VOD will be housed handle before the ladle of molten steel to put into vacuum tank airtight, vacuumized 2 minutes, Argon pipe bottom opening, stirring intensity is 2.3L/ (min.t).
(2) begin oxygen decarburization when the indoor air pressure of vacuum is reduced to 200mbar, the level two that oxygen blast flow and oxygen rifle height Danieli Off Mecc provide is controlled automatically.
In six stages of oxygen decarburization, each stage oxygen blast flow, blowing oxygen quantity, oxygen rifle height, ladle bottom Argon intensity and vacuum tightness are as follows:
| The oxygen blast stage | Oxygen blast flow Nm 3/h | Oxygen rifle height mm | Ladle argon-blown intensity L/ (min.t) | Vacuum tightness mbar |
| One two three four five six | 1325 1502 1484 1454 1252 1184 | 1605 1504 1504 1450 1450 1401 | 4.3 6.2 6.2 9.0 9.0 12.1 | 200 105 95 70 50 30 |
(3) stop oxygen blast when carbon content in the molten steel is 0.03, this moment, blowing oxygen quantity reached 748Nm
3, the 3 minutes final vacuum degree value of reaching capacity 0.6mbar, boiling is 23 minutes under this vacuum tightness, and ladle bottom Argon intensity is 16.2L/ (min.t);
(4) add ferrosilicon 450kg, lime 1755kg, fluorite material 500kg, with the chromium and the reduction of other metallic element of the oxidation of oxygen blast stage, the recovery time is 12 minutes, the vacuum tightness in the argon bottom-blowing intensity 15.5L/ (min.t), vacuum tank is 1mbar;
(5) add 180kg aluminium deep deoxidation, bottom blowing argon gas intensity is 13.2L/ (min.t), and the vacuum tightness in the vacuum tank is 2mbar, deaeration time 13 minutes;
(6) close bottom blowing and stir gas;
Molten steel face calmness after (7) 2 minutes is opened vacuum valve and is destroyed vacuum;
(8) open vacuum cover, the temperature of measuring molten steel is 1595 ℃, sampling, and the chemical ingredients (weight) after the decarburization of VOD ferritic stainless steel, the denitrogenation is:
C：0.004％ Si：0.11％ Mn：0.22％ P：0.019％
S：0.001％ Cr：18.35％ Mo：2.14％ N(ppm)：70
All the other are iron and unavoidable impurities.Meet technical requirements, the cast of coming out of the stove.72 minutes treatment times.
Embodiment three
The equipment of present embodiment and VOD starting condition require: 75 tons of upper dynamic VOD final vacuum≤1mbar, the maximum stirring intensity 15.5L/ (min.t) of steel ladle bottom argon blowing.The ladle freeboard is the top of the slag to the vertical range H of ladle upper edge is 1300mm, 1609 ℃ of molten steel initial temperatures, and thickness of slag layer is 50mm, and molten steel weight is 73.5 tons, and the smelting steel grade is 00Cr12Ti.
The chemical ingredients (weight) of molten steel was before VOD handled:
C：0.42％ Si：0.07％ Mn：0.35％ P：0.015％
S：0.009％ Cr：11.39％ N(ppm)：195
All the other are iron and unavoidable impurities.
The step of the super-purity ferrite stainless steel decarburization of present embodiment, the method for denitrogenation is as follows:
(1) VOD will be housed handle before the ladle of molten steel to put into vacuum tank airtight, vacuumized 3 minutes, Argon pipe bottom opening, stirring intensity is 2.0L/ (min.t).
(2) begin oxygen decarburization when the indoor air pressure of vacuum is reduced to 190mbar, the level two that oxygen blast flow and oxygen rifle height Danieli Off Mecc provide is controlled automatically.In six stages of oxygen decarburization, each stage oxygen blast flow, blowing oxygen quantity, oxygen rifle height, ladle bottom Argon intensity and vacuum tightness are as follows:
| The oxygen blast stage | Oxygen blast flow Nm 3/h | Oxygen rifle height mm | Ladle argon-blown intensity L/ (min.t) | Vacuum tightness mbar |
| One two three four five six | 1325 1552 1454 1404 1202 1124 | 1600 1500 1500 1450 1450 1400 | 4.3 7.2 7.2 9.5 9.5 12.1 | 190 125 90 75 50 40 |
(3) stop oxygen blast when carbon content in the molten steel is 0.03, this moment, blowing oxygen quantity reached 440Nm
3, the 2 minutes final vacuum degree value of reaching capacity 0.4mbar, boiling is 20 minutes under this vacuum tightness, and ladle bottom Argon intensity is 14.2L/ (min.t);
(4) add ferrosilicon 450kg, lime 1855kg, fluorite material 520kg, with the chromium and the reduction of other metallic element of the oxidation of oxygen blast stage, the recovery time is 10 minutes, the vacuum tightness in the argon bottom-blowing intensity 14.5L/ (min.t), vacuum tank is 1mbar;
(5) add 185kg aluminium deep deoxidation, bottom blowing argon gas intensity is 11.2L/ (min.t), and the vacuum tightness in the vacuum tank is 1mbar, deaeration time 10 minutes;
(6) close bottom blowing and stir gas;
Molten steel face calmness after (7) 2 minutes is opened vacuum valve and is destroyed vacuum;
(8) open vacuum cover, the temperature of measuring molten steel is 1570 ℃, sampling, and the chemical ingredients (weight) after the decarburization of VOD ferritic stainless steel, the denitrogenation is:
C：0.002％ Si：0.35％ Mn：0.36％ P：0.016％
S:0.001% Cr:11.35% N (ppm): 50 all the other be iron and unavoidable impurities.Meet technical requirements, come out of the stove and pour into a mould.61 minutes this stove treatment times
In the present specification:
Vertical range between oxygen rifle height oxygen rifle oxygen outlet and molten steel face.
VOD vacuum-oxygen decarbonizing technology is Vacuum Oxygen Decarburization
Vertical range between the ladle freeboard top of the slag and the ladle upper edge
Claims (1)
1, the smelting process of a kind of super-purity ferrite stainless steel decarburization, denitrogenation, it comprises following step successively:
(1) VOD will be housed handle before the ladle of molten steel to put into vacuum tank airtight, vacuumize, the interior air pressure of vacuum tank remains on 260-350mbar, opens BOTTOM ARGON BLOWING gas;
(2) begin oxygen decarburization when the air pressure in the vacuum tank is reduced to 200-250mbar, oxygen decarburization is divided into six stages, and each oxygen decarburization stage is controlled corresponding oxygen blast flow, blowing oxygen quantity, oxygen rifle height, ladle bottom stirring intensity and vacuum tightness;
(3) when the content of carbon in the molten steel is reduced to 0.03%-0.05%, stop oxygen blast, carry out high vacuum boiling, denitrogenation under decarburization and the high vacuum under high vacuum, when the vacuum tightness in the vacuum tank is not more than 1mbar, boiling time 〉=20 minute; Ladle bottom gas stirring intensity 〉=13L/ (min.t);
(4) add ferrosilicon, chromium and the reduction of other metallic element with the oxidation of oxygen blast stage, ferrosilicon add-on=molten steel terminal point requires silicone content * molten steel weight ÷ ferrosilicon silicon content ÷ ferrosilicon rate of recovery, add lime, fluorite material simultaneously, the lime of adding, the amount of fluorite are fluorite: 7kg/t, lime: 25kg/t, slag making, 10～15 minutes recovery times, the bottom blowing stirring intensity is greater than 10L/ (min.t), vacuum tightness≤5mbar
(5) add the aluminium deep deoxidation, Al add-on 2.5kg/t, stirring intensity be greater than 10L/ (min.t), vacuum tightness≤5mbar, deaeration time 5～10 minutes;
(6) alloy fine setting, 5～10 minutes even time of composition;
(7) close bottom blowing and stir gas;
(8) treat to open vacuum valve destruction vacuum after the molten steel face calmness.
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| CN110551874B (en) * | 2019-09-18 | 2021-08-24 | 舞阳钢铁有限责任公司 | Smelting method for improving vacuum aluminum recovery rate |
| WO2023000707A1 (en) * | 2021-07-23 | 2023-01-26 | 二重（德阳）重型装备有限公司 | Vanadium-controlled cr13 type hydroelectric stainless steel smelting method |
| CN113897531A (en) * | 2021-09-08 | 2022-01-07 | 三鑫重工机械有限公司 | Process for vacuum smelting of corrosion-resistant stainless steel by VOD method |
| CN113897531B (en) * | 2021-09-08 | 2022-12-13 | 三鑫重工机械有限公司 | Process for vacuum smelting of corrosion-resistant stainless steel by VOD method |
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