CN109280734B - Smelting method of medium and high alloy ultra-low phosphorus steel - Google Patents

Smelting method of medium and high alloy ultra-low phosphorus steel Download PDF

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CN109280734B
CN109280734B CN201811450857.8A CN201811450857A CN109280734B CN 109280734 B CN109280734 B CN 109280734B CN 201811450857 A CN201811450857 A CN 201811450857A CN 109280734 B CN109280734 B CN 109280734B
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slag
blowing
steel
phosphorus
smelting
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CN109280734A (en
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杨治争
赵逸群
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Baowu Group Echeng Iron and Steel Co Ltd
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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
    • C21C5/28—Manufacture of steel in the converter
    • C21C5/30—Regulating or controlling the blowing
    • C21C5/35—Blowing from above and through the bath
    • 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
    • C21C5/36—Processes yielding slags of special composition
    • 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
    • C21C7/064—Dephosphorising; Desulfurising
    • C21C7/0645—Agents used for dephosphorising or desulfurising
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon Steel Or Casting Steel Manufacturing (AREA)

Abstract

The invention discloses a smelting method of medium and high alloy ultra-low phosphorus steel, which adopts a converter double-slag deep dephosphorization process, reduces the oxygen pressure to 0.75-0.80 MPa when smelting first slag in a converter, improves the dephosphorization efficiency of the first slag smelting by using a method of reducing the oxygen pressure at low temperature by molten iron, and pours out 55-70% of dephosphorization slag when the first slag smelting is finished; during the smelting of the second slag, a special barium-based dephosphorizing agent is adopted, the dephosphorizing efficiency of the smelting of the second slag is further improved by utilizing the characteristic of high phosphorus capacity of the barium-based dephosphorizing agent, and meanwhile, the formed barium-based dephosphorizing slag has high stability, so that the phosphorus slag rephosphorization in the tapping process and after tapping can be effectively prevented, and the phosphorus content in the finished steel grade can be ensured to meet the requirement of ultra-low phosphorus steel; the method realizes the low-cost stable smelting production of the ultra-low-phosphorus medium-high alloy steel, provides reliable metallurgical process and effect guarantee for the research and development of related varieties, and also provides a solid foundation for the research and development of other ultra-low-phosphorus steel types.

Description

Smelting method of medium and high alloy ultra-low phosphorus steel
Technical Field
The invention relates to the technical field of steel materials, in particular to a smelting method of medium and high alloy ultra-low phosphorus steel.
Background
At present, the steel grade with the phosphorus content less than or equal to 0.005 percent is generally called ultra-low phosphorus steel.
Generally, phosphorus is a harmful element in steel, can improve the fluidity of molten steel, obviously enlarges a solid-liquid two-phase region, causes serious primary segregation of the molten steel in the solidification process, and narrows a gamma solid solution region which is easy to segregate in a solid state. Phosphorus is segregated among crystal grains in the solidification process of the steel to form a high-phosphorus brittle layer, so that the plasticity and the toughness of the steel are reduced, brittle cracks are easy to generate in the steel, and the low-temperature high-phosphorus brittle layer is particularly obvious. Particularly in the combination of properties, phosphorus also reduces the weldability of steel and is also susceptible to hydrogen induced cracking and stress corrosion cracking. During the heat treatment, phosphorus increases the temper embrittlement sensitivity of the steel, causing cold embrittlement. The surface quality of the steel is also adversely affected during production.
The conditions of strong oxidizing environment, large slag quantity, high-alkalinity slag system, top-bottom combined blowing stirring and the like in the smelting process of the converter are favorable factors for molten steel dephosphorization, so the dephosphorization is one of the main tasks of the converter smelting, the dephosphorization through the converter smelting is also the current path with the best effect, the lowest cost and the most extensive application, the oxidative dephosphorization belongs to an exothermic reaction, and the molten steel temperature at the earlier stage of the converter smelting is relatively lower, thereby being more beneficial to efficient dephosphorization.
Because the oxidative dephosphorization reaction of the converter is an endothermic process, and the temperature of molten iron entering the converter is generally below 1400 ℃, the earlier-stage dephosphorization of the converter has relatively better thermodynamic conditions. In actual production practice, there are a large number of successful cases of deep dephosphorization of molten steel based on a converter double slag method and a duplex method, although the duplex steelmaking method can smelt molten steel to an ultra-low phosphorus level of below 0.003%, the requirement on equipment is high, the smelting process is complex, the production cycle is long, the overall cost is high, and the method is not the mainstream of steelmaking production in the industry at present, and the smelting method for producing ultra-low phosphorus steel by deep dephosphorization of a single converter can be summarized as follows through query results of a platform of a Chinese and foreign patent database and contents of related papers in a Chinese periodical network database:
1) the low-phosphorus molten iron with the phosphorus content lower than 0.12 percent is adopted, and better raw material conditions are provided for the production of ultra-low phosphorus.
2) The method adopts a twice or three-time slagging smelting process, alkaline high-oxidation dephosphorization slag is produced in a lower temperature range in the early smelting stage through the control of the lance position of an oxygen lance and the oxygen supply intensity, the early-stage phosphorus-rich slag is poured out through a converter, and then decarburization smelting is carried out (actually, the three-time slagging cannot be stably realized in the current converter smelting production due to the temperature control).
3) The tapping temperature is properly reduced at the smelting end point of the converter, better dephosphorization thermodynamic conditions are ensured, tapping and slag stopping are well carried out, and rephosphorization in the subsequent refining process is reduced.
Aiming at the smelting of medium and high alloy steel containing 5-10% of the total amount of Ni, Cr and Mn, a nickel plate can enter a furnace along with scrap steel due to the large total amount of alloy, but obvious phosphorus increasing phenomenon is easy to occur when chromium and manganese alloy are added in the tapping process, the control of the phosphorus content of a finished product is more difficult, particularly the smelting difficulty of medium and high alloy steel with the finished product target phosphorus less than or equal to 0.005% is high, and the target of ultra-low phosphorus content is difficult to achieve by adopting the conventional double-slag smelting method.
Disclosure of Invention
The invention aims to provide a smelting method of medium and high alloy ultra-low phosphorus steel, aiming at the problem that the target requirement of ultra-low phosphorus content of a specific steel product cannot be met by adopting a conventional smelting method in the smelting process of the medium and high alloy (Ni + Cr + Mn is more than or equal to 5% and less than or equal to 10%) steel at present. Under the condition of single-converter double-slag smelting, by controlling the raw material components and temperature of molten iron, optimizing design of an oxygen lance, controlling the lance position and oxygen supply intensity, adding a slag adjusting agent and a dephosphorizing agent, controlling the tapping process and the like, the content of tapping phosphorus reaches 0.0030-0.0035% and the content of finished phosphorus reaches 0.0035-0.0040% under the condition that the content of phosphorus in the molten iron entering a furnace is 0.08-0.12%.
The invention relates to a smelting method of medium and high alloy ultra-low phosphorus steel, which comprises the following steps:
(1) adding a proper amount of scrap steel into a converter according to a conventional method, proportionally adding enough ferronickel alloy into the converter, and then adding molten iron, wherein the temperature of the molten iron before adding into the converter is more than or equal to 1250 ℃, the mass percent content of silicon in the molten iron is 0.3-0.6%, and the mass percent content of phosphorus in the molten iron is 0.08-0.12%;
(2) when the first slagging blowing is started, firstly adding active lime according to 15-18 kg/t steel, adding 4-6 kg/t steel limestone within 180s from the beginning of blowing, and then controlling the lance position to be 1.65m to carry out low-strength blowing, wherein the oxygen pressure is controlled to be 0.75-0.8 MPa, and the oxygen supply strength is controlled to be 2.5-2.8 Nm3The bottom blowing mode is super-strong, and the bottom blowing strength is 0.06-0.08 Nm3T.min; adding raw dolomite and iron scale for cooling within 180-300 s of blowing, wherein the total addition amount of the raw dolomite and the iron scale is 5-8 kg/t steel, the raw dolomite and the iron scale need to be added within 120s before the first blowing is finished, finishing the first blowing when the blowing is finished to 420-480 s, controlling the finishing temperature of the blowing to be 1340-1380 ℃, and controlling the binary alkalinity CaO/SiO of the slag to be CaO/SiO22.0-2.5 percent, the TFeO content in the slag is 12-16 percent, after the process is finished, the furnace is lifted and inverted, and 55-70 percent of the phosphorus-rich slag in the first blowing is poured out;
(3) shaking the furnace body, performing secondary slagging blowing, adding 12-15 kg/t of active lime into the converter in 2 batches at the beginning, controlling the gun position at 1.5m, the oxygen pressure at 0.95-1.0 MPa and the oxygen supply intensity at 3.2-3.5 Nm3At/t.min, the bottom blowing is in a strong bottom blowing mode, and the bottom blowing strength is 0.04-0.06 Nm3And (2) after blowing for 180s, adding a barium-based dephosphorizing agent into the furnace in 2-3 batches, wherein the total addition amount of the barium-based dephosphorizing agent is 10-15 kg/t of steel, simultaneously carrying out decarburization of the converter and subsequent operation, adding all slag materials within 180s before oxygen blowing is finished, controlling the total oxygen blowing time in the whole smelting process to be 900-960 s, and controlling the binary alkalinity CaO/SiO of the final slag23.2 to 3.8, the end point carbon content of the converter is less than or equal to 0.05 percent, the end point temperature is 1600 to 1620 ℃, and the end point phosphorus contentThe amount is 0.0030-0.0035%;
(4) the method is characterized in that silicon-manganese alloy, ferromanganese alloy, ferrochrome alloy and other alloys are sequentially added in the tapping process, a sliding plate is adopted to block slag and tap, the slag discharging amount is strictly controlled, the slag thickness in a molten steel tank after tapping is less than or equal to 40mm, the stability of barium phosphate generated by a barium-based dephosphorizing agent is higher than that of calcium phosphate, the slag discharging amount is small, the occurrence of the rephosphorization condition in the subsequent refining process can be effectively reduced, and the mass percentage of phosphorus in the finished steel grade is 0.0035-0.0040%.
The barium-based dephosphorizing agent comprises the following components in percentage by mass: BaCO3：60～65%，CaCO3：15～20，SiO2: 8-10%, FeO: 5-8, barium sulfate: 3-5%, and the sum of the raw materials is 100%.
The converter is a 130t top-bottom combined blown converter.
The process principle of the invention is as follows: by utilizing a converter double-slag smelting process, the oxygen pressure is reduced during the first slag smelting, the dephosphorization efficiency is improved at low temperature and low oxygen pressure, the barium-based dephosphorization agent is added during the second slag smelting, the dephosphorization efficiency during the second slag smelting is improved by utilizing the characteristic of high phosphorus capacity of the barium-based dephosphorization agent, and the rephosphorization during the tapping process and the refining process after tapping is reduced by utilizing the characteristic of high stability of the barium-based dephosphorization slag, so that the deep dephosphorization of the converter is realized, and the goal that the phosphorus content at the smelting end point is less than or equal to 0.0035 percent is reached; and meanwhile, the sliding plate is combined with slag stopping and tapping, so that the slag discharge amount is reduced, and the mass percentage of phosphorus in the finished steel is 0.0035-0.0040%.
Compared with the traditional smelting method, the method of the invention has the following advantages:
(1) the converter double-slag deep dephosphorization process, the application of the tapping slide plate for pushing off slag, the application of the barium-based dephosphorization slag after tapping and other processes and equipment are combined with slag charge, so that the deep dephosphorization process is controllable, and the result is stable;
(2) the phosphorus content of the molten steel at the smelting end point of the converter is in the range of 0.0030-0.0035%, the phosphorus content of the finished product is in the range of 0.0035-0.0040%, and the phosphorus content control is superior to the existing level of similar steel in the industry.
The method can realize the stable smelting production of the medium and high alloy steel with ultralow phosphorus (finished phosphorus of 0.004 percent) at lower cost, and provides reliable metallurgical process and effect guarantee for the research and development of related varieties; meanwhile, the method of the invention provides a solid foundation for the research and development of other ultra-low phosphorus steel grades while improving the technical level of the steel-making link.
Detailed Description
In order to better explain the technical scheme of the invention, the technical scheme of the invention is further described below by combining specific examples, and in order to better embody the inventive step of the invention, the following examples 1 to 5 are specific cases of smelting by the method of the invention in a 130t top-bottom combined blown converter, and comparative examples 1 to 2 are specific cases of adopting a conventional double slag smelting method.
The following table 1 is a list of values of main process parameters in the smelting methods of the examples and comparative examples of the present invention.
Table 2 below is a value list of the formula of the barium-based dephosphorizing agent in each example of the present invention.
The invention relates to a smelting method of medium and high alloy ultra-low phosphorus steel, which comprises the following steps:
(1) adding a proper amount of scrap steel into a converter according to a conventional method, proportionally adding enough ferronickel alloy into the converter, and then adding molten iron, wherein the temperature of the molten iron before adding into the converter is more than or equal to 1250 ℃, the mass percent content of silicon in the molten iron is 0.3-0.6%, and the mass percent content of phosphorus in the molten iron is 0.08-0.12%; the converter used in this example was a 130t top-bottom combined blown converter;
(2) when the first slagging blowing is started, firstly adding active lime according to 15-18 kg/t steel, then adding 4-6 kg/t steel limestone within 180s from the beginning of blowing, and then controlling the gun position to be 1.65m to carry out low-strength blowing, wherein the oxygen pressure is controlled to be 0.75-0.8 MPa, and the oxygen supply strength is controlled to be 2.5-2.8 Nm3The bottom blowing mode is super-strong, and the bottom blowing strength is 0.06-0.08 Nm3T.min; adding raw dolomite and iron scale for cooling within 180-300 s of blowing, wherein the total addition amount of the raw dolomite and the iron scale is 5-8 kg/t steel, the raw dolomite and the iron scale need to be added within 120s before the first blowing is finished, finishing the first blowing when the blowing is finished to 420-480 s, controlling the finishing temperature of the blowing to be 1340-1380 ℃, and controlling the binary alkalinity CaO/SiO of the slag to be CaO/SiO22.0-2.5, and the TFeO content in the slag is 12-16%, and the process is finishedLifting the gun and turning down the furnace, and pouring out 55-70% of the phosphorus-rich slag obtained in the first converting;
(3) shaking the furnace body, performing secondary slagging blowing, adding 12-15 kg/t of active lime into the converter in 2 batches at the beginning, controlling the gun position at 1.5m, the oxygen pressure at 0.95-1.0 MPa and the oxygen supply intensity at 3.2-3.5 Nm3At/t.min, the bottom blowing is in a strong bottom blowing mode, and the bottom blowing strength is 0.04-0.06 Nm3And (2) after blowing for 180s, adding a barium-based dephosphorizing agent into the furnace in 2-3 batches, wherein the total addition amount of the barium-based dephosphorizing agent is 10-15 kg/t of steel, simultaneously carrying out decarburization and subsequent operation of the converter, adding all slag materials within 180s before oxygen blowing is finished, and controlling the binary alkalinity CaO/SiO of the final slag23.2-3.8 percent, the end point carbon content of the converter is less than or equal to 0.05 percent, the end point temperature is 1600-1620 ℃, and the end point phosphorus content is 0.0030-0.0035 percent;
(4) the method is characterized in that silicon-manganese alloy, ferromanganese alloy, ferrochrome alloy and other alloys are sequentially added in the tapping process, a sliding plate is adopted to block slag and tap, the slag discharging amount is strictly controlled, the slag thickness in a molten steel tank after tapping is less than or equal to 40mm, the stability of barium phosphate generated by a barium-based dephosphorizing agent is higher than that of calcium phosphate, the slag discharging amount is small, the occurrence of the rephosphorization condition in the subsequent refining process can be effectively reduced, and the mass percentage of phosphorus in the finished steel grade is 0.0035-0.0040%.
The barium-based dephosphorizing agent comprises the following components in percentage by mass: BaCO3：60～65%，CaCO3：15～20，SiO2: 8-10%, FeO: 5-8, barium sulfate: 3-5%, and the sum of the raw materials is 100%.
TABLE 1 tabulation of values of main process parameters for each example of the invention and comparative example
Figure DEST_PATH_IMAGE002
TABLE 2 formulation ingredient list of barium-based dephosphorizing agent in each example of the present invention
Figure DEST_PATH_IMAGE004
And (4) analyzing results: through the comparison of the process parameters of the examples 1-5 and the comparative examples 1 and 2 and the comparison of the phosphorus content in the finished steel grade, it can be seen that by adopting the smelting method, the phosphorus content in the finished steel grade is stabilized at 0.0035-0.0040 percent, and the phosphorus content of the ultra-low phosphorus steel is met, while the phosphorus content in the comparative examples 1 and 2 is far higher than 0.0040 percent, and the phosphorus content of the ultra-low phosphorus steel cannot be met. The above result is also caused by the difference between the smelting processes of the embodiments 1 to 5 of the present invention and the smelting processes of the comparative examples 1 and 2, and the specific analysis is as follows: in the embodiments 1 to 5 of the invention, the oxygen pressure is reduced to 0.75 to 0.80MPa during the first slag smelting of the converter, while in the comparative examples 1 to 2, the conventional oxygen pressure is 0.95 to 1.0MPa, so that the oxygen pressure is reduced, dephosphorization is facilitated when the temperature of molten iron is lower, the dephosphorization efficiency during the first slag smelting is improved, and 55 to 70 percent of dephosphorization slag is poured out when the first slag smelting is finished; during smelting of the second slag, a special barium-based dephosphorizing agent is adopted, the dephosphorizing efficiency of smelting of the second slag is further improved by utilizing the characteristic of high phosphorus capacity of the barium-based dephosphorizing agent, meanwhile, the formed barium-based dephosphorizing slag can effectively prevent rephosphorization, and further the phosphorus content in the finished steel grade is ensured to meet the requirement of ultra-low phosphorus steel.
The above embodiments are merely exemplary for illustrating the technical solutions of the present invention, and do not limit the present invention in any way, and any equivalent replacement, similar improvement, enlargement or reduction of the method of the present invention based on the principle of the claims of the present invention should be considered as falling within the protection scope of the claims of the present invention.

Claims (1)

1. A smelting method of medium and high alloy ultra-low phosphorus steel is characterized by comprising the following steps:
(1) adding a proper amount of scrap steel into a converter according to a conventional method, proportionally adding enough ferronickel alloy into the converter, and then adding molten iron, wherein the temperature of the molten iron before adding into the converter is more than or equal to 1250 ℃, the mass percent content of silicon in the molten iron is 0.3-0.6%, and the mass percent content of phosphorus in the molten iron is 0.08-0.12%;
(2) when the first slagging blowing is started, firstly adding active lime according to 15-18 kg/t steel, adding 4-6 kg/t steel limestone within 180s from the beginning of blowing, then controlling the gun position to be 1.65m for low-strength blowing, and controlling the oxygen pressure to be 0.75-0.8 MPaThe oxygen supply intensity is 2.5-2.8 Nm3The bottom blowing mode is super-strong, and the bottom blowing strength is 0.06-0.08 Nm3T.min; adding raw dolomite and iron scale for cooling within 180-300 s of blowing, wherein the total addition amount of the raw dolomite and the iron scale is 5-8 kg/t steel, the raw dolomite and the iron scale need to be added within 120s before the first blowing is finished, finishing the first blowing when the blowing is finished to 420-480 s, controlling the finishing temperature of the blowing to be 1340-1380 ℃, and controlling the binary alkalinity CaO/SiO of the slag to be CaO/SiO22.0-2.5 percent, the TFeO content in the slag is 12-16 percent, after the process is finished, the furnace is lifted and inverted, and 55-70 percent of the phosphorus-rich slag in the first blowing is poured out;
(3) shaking the furnace body, performing secondary slagging blowing, adding 12-15 kg/t of active lime into the converter in 2 batches at the beginning, controlling the gun position at 1.5m, the oxygen pressure at 0.95-1.0 MPa and the oxygen supply intensity at 3.2-3.5 Nm3At/t.min, the bottom blowing is in a strong bottom blowing mode, and the bottom blowing strength is 0.04-0.06 Nm3And (2) after blowing for 180s, adding a barium-based dephosphorizing agent into the furnace in 2-3 batches, wherein the total addition amount of the barium-based dephosphorizing agent is 10-15 kg/t of steel, simultaneously carrying out decarburization and subsequent operation of the converter, adding all slag materials within 180s before oxygen blowing is finished, and controlling the binary alkalinity CaO/SiO of the final slag23.2-3.8 percent, the end point carbon content of the converter is less than or equal to 0.05 percent, the end point temperature is 1600-1620 ℃, and the end point phosphorus content is 0.0030-0.0035 percent;
(4) silicon-manganese alloy, ferromanganese alloy and ferrochrome alloy are sequentially added in the tapping process, a sliding plate is adopted to block slag and tap, the slag discharging amount is strictly controlled, the slag thickness in a molten steel tank after tapping is less than or equal to 40mm, the stability of barium phosphate generated by a barium-based dephosphorizing agent is higher than that of calcium phosphate, and the slag discharging amount is small, so that the occurrence of a rephosphorization condition in the subsequent refining process can be effectively reduced, and the mass percentage content of phosphorus in the finished steel grade is 0.0035-0.0040%;
the barium-based dephosphorizing agent comprises the following components in percentage by mass: BaCO3：60～65%，CaCO3：15～20，SiO2: 8-10%, FeO: 5-8, barium sulfate: 3-5%, and the sum of the raw materials is 100%.
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