CN110331255B - Precipitation deoxidation method of low-carbon aluminum killed steel - Google Patents
Precipitation deoxidation method of low-carbon aluminum killed steel Download PDFInfo
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- CN110331255B CN110331255B CN201910732197.0A CN201910732197A CN110331255B CN 110331255 B CN110331255 B CN 110331255B CN 201910732197 A CN201910732197 A CN 201910732197A CN 110331255 B CN110331255 B CN 110331255B
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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
- C21C7/06—Deoxidising, e.g. killing
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- Treatment Of Steel In Its Molten State (AREA)
Abstract
The invention discloses a precipitation deoxidation method of low-carbon aluminum killed steel, which comprises the steps of selecting calcium carbonate with the calcium oxide content of more than 50%, and crushing the calcium carbonate to 10mm for later use; sodium salt: one of sodium fluoride, sodium fluoroaluminate, sodium chloride, sodium carbide and sodium carbonate is pulled to a vertical mill for standby; selecting scaly graphite with carbon content more than 90%, and carrying to a vertical mill for standby; sodium salt and graphite are mixed according to the weight ratio of 1: 1, mixing, grinding to 150 meshes in a vertical mill, and discharging; taking calcium oxide as an aggregate and a mixture of sodium salt and graphite as a powder material, pressing the powder material into balls on a high-pressure dry powder double-roller ball press machine, and pulling and transporting the ball-shaped deoxidized material product with the granularity of 30-50 mm to a steel-making production line for later use; and (3) beginning to tap steel from the converter, when the weight of molten steel in a ladle reaches 15 tons, adding the deoxidizing material product in an amount of 0.8-1.5 kg per ton of steel, then adding an aluminum block or an aluminum-iron and aluminum-manganese-iron alloy for deoxidation and lime for deoxidation, and adding the product before the tapping of the converter is finished.
Description
Technical Field
The invention relates to metallurgy and mechanochemical reaction principles, in particular to a precipitation deoxidation method for low-carbon aluminum killed steel.
Background
The precipitation deoxidation of the steel making has two tasks, one is to convert free oxygen or a pumice body in the middle of the molten steel into an oxide by utilizing a material with the affinity with oxygen being larger than that of an iron element, and the other task is to remove the oxide generated in the deoxidation process from the middle of the molten steel.
The metallic elements having a higher affinity for oxygen than that of iron are mostly elements having a metal activity order before iron, most of which are mainly alkali metal elements, and the non-metallic elements are represented by Si and C. The precipitation deoxidation of the molten steel adopts a process means of carrying out alloying and deoxidation together, most of oxides generated in the precipitation deoxidation process exist in the molten steel, and the oxides need to be removed by technical means of blowing argon into the molten steel, adding low-melting-point deoxidation slag for slag washing and the like.
The search literature discloses: (1) the "recognization of deoxidation of aluminum for steel" published in "journal of iron and Steel research" by the first edition of the society of research, Zhao Qin, Zhao, Zhan, etc. of the university of Xian traffic, among the papers, "pure aluminum is replaced by SiBaAl alloy,The ferrosilicon-aluminum is used as final deoxidizing agent for steel making, and can completely meet the requirement of steel deoxidation, and the deoxidation capability of barium is 2 orders of magnitude greater than that of aluminum. Barium can also adjust the density and melting point of inclusions, improve the wettability and contact surface energy of molten steel to the inclusions, and enable the inclusions to be easily removed. "is expressed in terms of content; (2) a paper entitled "influence of melt structure on deoxidation rate of ladle slag" published in Zhongnan university proceedings of 2011 No. 1 by Zhang Shi, Min Yi, Wang German Yong and Jiangmeng203Controlling the content and the alkalinity; the iron ion diffusion is a control link of the slag deoxidation reaction, and the structural analysis of the experimental slag melt shows that the iron ion diffusion is accompanied with Al203The content is increased, the polymerization degree of the slag is enhanced, the viscosity is increased, and the average diffusion size of iron ions is reduced; with the increase of alkalinity, the polymerization degree of the slag is weakened, the viscosity is reduced, and the average diffusion size of iron ions is increased: diffusion coefficient of iron ion with Al203The content and alkalinity increase and decrease at first, and the change trend of the content and alkalinity is consistent with the change trend of the initial deoxidation rate of the slag. In order to improve the deoxidation rate of the ladle slag in the LF refining process, the ladle slag component adjustment target before the LF refining is as follows: w (CaO)/w (Si 0)2)=4～5，w(Al203) And =18% -20%. "is expressed in terms of the content. (3) Li Yang, Jiang Zhou Hua and Jiang Hua, etc. published in the Steel research institute in 5 th phase 2002 as CaO-Al2O3The influence of the refining slag on the deoxidation of molten steel is disclosed in the middle of the paper, namely that the total oxygen content of the molten steel is basically along with Al in the refining slag under the condition of using aluminum to deoxidize203The content of the additive increases along with the increase of CaF in the refining slag2The content is increased, and the total oxygen content of the molten steel tends to increase firstly and decrease secondly. "is expressed in terms of the content. (4) Chenxiang in journal of "iron alloy" of No. 1 of 2007, there is published a composition entitled "optimum composition of composite deoxidizer" in which the melting point of deoxidation product is low, so as to exert the effect of easy collision, growth, upward floating and removal, not only the residual inclusion in steel is less, but also the generation of solid deoxidation product (Al) is avoided2O3) High content of residual Al, and less secondary oxidationAnd the phenomenon of water gap blockage. "is expressed in terms of the content.
As can be seen from the above documents, in the process of deoxidizing molten steel, aluminum oxide enters into the top slag to increase the oxygen content in the molten steel, and aluminum is used for deoxidizing to remove Al generated by the deoxidation of aluminum2O3Inclusion, elimination of Al during casting2O3The gathering blocks the water gap, which is the core content of the deoxidation of the aluminum killed steel.
Disclosure of Invention
The invention aims to provide a precipitation deoxidation method of low-carbon aluminum killed steel, which can convert free oxygen and a sorbite of molten steel into an oxide and can utilize small bubbles generated by a deoxidizer to adhere small-particle Al generated by aluminum deoxidation2O3Floating upwards, and removing the deoxidized product from the middle of the molten steel as much as possible.
The invention aims to realize the precipitation deoxidation method of the low-carbon aluminum killed steel, and the steel comprises the following components: si <0.03, C <0.06, Al 0.02-0.06, Mn 0.25-0.60; the precipitation deoxidation material used in the method is prepared according to the following steps:
01. selecting calcium carbonate with the calcium oxide content of more than 50 percent, and crushing the calcium carbonate to 10mm for later use;
02. sodium salt: one of sodium fluoride, sodium fluoroaluminate, sodium chloride, sodium carbide and sodium carbonate is pulled to a vertical mill for standby;
03. selecting scaly graphite with carbon content more than 90%, and carrying to a vertical mill for standby;
04. sodium salt and graphite are mixed according to the weight ratio of 1: 1, mixing, grinding to 150 meshes in a vertical mill, and discharging;
05. the method comprises the following steps of (1) pressing a mixture of sodium salt and graphite as a powder material on a high-pressure dry powder double-roller ball press to produce a spherical deoxidation material product with the granularity of 30-50 mm, wherein the spherical deoxidation material product meets the following requirements in the component range: ca + Mg + Na is less than 30, TC is less than 25, and then the steel is pulled to a steel-making production line for standby;
the deoxidation method comprises the following operation steps: and (3) beginning to tap steel from the converter, when the weight of molten steel in a ladle reaches 15 tons, adding the deoxidizing material product in an amount of 0.8-1.5 kg per ton of steel, then adding an aluminum block or an aluminum-iron and aluminum-manganese-iron alloy for deoxidation and lime for deoxidation, and adding the product before the tapping of the converter is finished.
The inventors have found through studies and experiments that a product formed by a decomposition reaction of a sodium salt containing a specific proportion of Al, added to molten steel, can react with Al2O3And Si02The reaction is carried out to generate sodium aluminate and sodium silicate with low melting points, and 8CaO & Na can be generated under the condition of calcium oxide2O·Al2O3、3CaO·2Na2O·5Al2O3、2Na2O·CaO·3SiO2、Na2O·3CaO·6SiO2、Na2O·2CaO·3SiO2Low melting point phase with melting point lower than 1540 deg.C, and is helpful for Al in molten steel2O3And Si02And floating is removed, and even if the floating is not generated, the floating is not accumulated in a water gap area in the process of casting molten steel, so that the problem of nodulation is avoided. In addition, the inventor also finds that in the argon blowing process for steelmaking, argon gas of molten steel is blown from the bottom, impurities in the middle of the molten steel are removed by two modes of removing large-particle impurities by means of large-bubble wake flow and removing fine-particle impurities by means of small-bubble adhesion, but an argon blowing dead zone which cannot be reached by argon gas blowing exists in the middle of an argon blowing ladle, and the impurities in the dead zone are difficult to remove, so the inventor proposes a molten steel comprehensive sodium treatment technology, namely, sodium salt and scaly graphite are adopted, sodium salt (any one of sodium carbide, sodium chloride, sodium fluoride, sodium carbonate and the like) and carbon are mixed and ground by a powder processing technology, the characteristics of the graphite are utilized, under the condition of mechanical force chemical reaction, the graphite and the sodium salt are synthesized into a mixture with polar characteristics, then carbonate is added to produce a composite deoxidizer, and the deoxidizer is matched with metal aluminum in the production process of aluminum killed steel, not only can complete the basic tasks of precipitation deoxidation: free oxygen and the sorbite of the molten steel are converted into oxide, and small bubbles generated by a deoxidizer can be utilized to adhere small-particle Al generated by aluminum deoxidation2O3Floating to remove the deoxidized product from the steel as much as possibleThe liquid is removed, the impurities which are not removed are removed, and a low-melting-point substance can be formed by a sodium treatment technology, so that the problem of nodulation generated in the casting process of the molten steel in a continuous casting machine is solved, namely the sodium treatment technology shows the advantages of technical progress. Wherein the component range of the precipitation deoxidizer is shown in the following table 1:
| Ca+Mg+Na | TC |
| <30 | <25 |
the technical principle and innovation points of the invention are as follows:
the technical principle and innovation points of the invention are based on the following points:
01. the inventor adopts a carbon-containing material as a component of a composite deoxidizer, adopts the principle of carbon deoxidation, reduces the concentration of free oxygen in molten steel, and reduces Al generated by aluminum deoxidation2O3The inclusions are simultaneously utilized, CO small bubbles generated by carbon deoxidation are utilized, and Al generated by aluminum deoxidation is adhered2O3The particles float upwards. In order to prevent the problem that the carbon-containing material is slow in reaction and causes the recarburization of the molten steel, the inventor adopts carbonate as a means for improving the carbon deoxidation reaction speed and increasing the reaction interface, and the invention is the first innovation point.
02. The inventor finds that: the melting points of the five sodium salts of sodium fluoride, sodium fluoroaluminate, sodium chloride, sodium carbide and sodium carbonate are all lower than 1009 ℃, and after the sodium salts are added into the middle of molten steel, the following reactions occur:
[Na3AlF6]→3[NaF]+[AlF3]
[NaF]→[Na+]+[ F-]
[AlF3]→[Al3+]+3[F-]
[Na2C2]+3[O]=[Na2O]+2{CO}↑
[Na2CO3]→[Na2O]+{CO2}↑
[NaCl]→[Na+]+[Cl-]
the gas generated by the reaction is also the kinetic condition for stirring the molten steel and expanding the deoxidation reaction interface, and fluorine ions and chloride ions can react with SiO2、Al2O3CaO, MgO, etc. to produce a low melting point substance. Wherein the chlorine reaction product includes CaClF and Ca3OCl4The slag is a liquefying agent of the slag, is in a liquid state in the molten steel, is easy to float upwards, and can adsorb Al generated by aluminum deoxidation in the floating process2O3The impurities float upwards together to achieve the purpose of removing.
03. The inventors have found that the sodium salt remaining in the molten steel can be mixed with Al without floating up by adding a sodium salt-containing substance into the molten steel2O3Small particles react to generate 8CaO & Na2O·Al2O3、3CaO·2Na2O·5Al2O3The substances with low melting points are beneficial to eliminating Al in molten steel flowing through a water gap slow flow region in the process of casting aluminum killed steel by a continuous casting machine2O3The agglomeration problem caused by the aggregation, and the low-melting-point inclusions which belong to plastic inclusions can reduce the Al remaining in the molten steel2O3Damage caused by rigid inclusions.
04. In the history of metallurgy, sodium salt is adopted to carry out desulfurization on molten iron, because the environment is polluted, and the corrosion on refractory materials is eliminated, the inventor aims at the problem, adopts composite material addition and content control means to solve the problem, namely, a carbon adding measure is adopted, bubbles generated by carbon deoxidation are used, and small-particle Al is adhered to2O3And the sodium salt reacts with a calcareous material added in the middle of the sodium salt, so that the problem of pollution caused by volatilization and separation of the sodium salt is solved.
05. The invention adopts the technology of eliminating the argon blowing dead zone by the micro bubbles, and is also an innovation in the technical means.
06. Decomposition products of sodium salt in molten steel, F ion and chloride ion, and Na2O has the function of oxidizing Si in molten steel, and is beneficial to controlling the content of silicon in the molten steel by using aluminum killed steel.
The invention adds the materials containing sodium salt and calcium salt according to a certain proportion by utilizing the mechanochemical reaction principle to produce the deoxidizing material in the molten steel deoxidizing process, and the deoxidizing material is used as the deoxidizing material in the converter or electric furnace tapping process, and has better effects on the deoxidizing of low-carbon aluminum killed steel, the purifying of molten steel and the relieving of nodulation in the casting process.
Detailed Description
The invention takes the production of low-carbon aluminum killed steel by a 300-ton converter in a certain factory as an example, and the component requirements of the steel grade are as follows: si <0.03, C <0.06, Al 0.02-0.06, Mn 0.25-0.60; the preparation process and the use process of the precipitation deoxidation material are as follows:
1. selecting calcium carbonate with the calcium oxide content of more than 50 percent, and crushing the calcium carbonate to 10mm for later use;
2. sodium salt: one of sodium fluoride, sodium fluoroaluminate, sodium chloride, sodium carbide and sodium carbonate is pulled to a vertical mill for standby;
3. selecting scaly graphite with carbon content more than 90%, and carrying to a vertical mill for standby;
4. sodium salt and graphite are mixed according to the weight ratio of 1: 1, mixing, grinding to 150 meshes in a vertical mill, and discharging;
5. the method comprises the following steps of (1) pressing a mixture of sodium salt and graphite as a powder material on a high-pressure dry powder double-roller ball press to produce a ball with the granularity of 30-50 mm, wherein the range of the components of the ball meets the following requirements: ca + Mg + Na is less than 30, TC is less than 25, and then the steel is pulled to a steel-making production line for standby;
and (3) when tapping of the converter is started, when the molten steel in a steel ladle reaches 15 tons, adding the product, wherein the adding amount is 0.8-1.5 kg per ton of steel, then adding an aluminum block or an aluminum-iron and aluminum-manganese-iron alloy for deoxidation, adding lime for deoxidation, and adding the product before the tapping of the converter is finished.
Claims (1)
1. A precipitation deoxidation method for low-carbon aluminum killed steel comprises the following components: si <0.03, C <0.06, Al 0.02-0.06, Mn 0.25-0.60; the method is characterized in that: firstly, the precipitation deoxidation material used in the method is prepared according to the following steps:
A. selecting calcium carbonate with the calcium oxide content of more than 50 percent, and crushing the calcium carbonate to 10mm for later use;
B. sodium salt: one of sodium fluoride, sodium fluoroaluminate, sodium chloride, sodium carbide and sodium carbonate is pulled to a vertical mill for standby;
C. selecting scaly graphite with carbon content more than 90%, and carrying to a vertical mill for standby;
D. sodium salt and graphite are mixed according to the weight ratio of 1: 1, mixing, grinding to 150 meshes in a vertical mill, and discharging;
E. the method comprises the following steps of (1) pressing a mixture of sodium salt and graphite as a powder material on a high-pressure dry powder double-roller ball press to produce a spherical deoxidation material product with the granularity of 30-50 mm, wherein the spherical deoxidation material product meets the following requirements in the component range: ca + Mg + Na is less than 30, TC is less than 25, and then the steel is pulled to a steel-making production line for standby;
secondly, the operating steps of the deoxidation method are as follows: and (3) beginning to tap steel from the converter, when the weight of molten steel in a ladle reaches 15 tons, adding the deoxidizing material product in an amount of 0.8-1.5 kg per ton of steel, then adding an aluminum block or an aluminum-iron and aluminum-manganese-iron alloy for deoxidation and lime for deoxidation, and adding the product before the tapping of the converter is finished.
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