CN111945056A - High-sulfur steel and preparation method thereof - Google Patents
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Abstract
The invention discloses high-sulfur steel and a preparation method thereof, wherein the preparation method comprises the following steps: primary refining: carrying out primary smelting treatment on smelting raw materials to obtain molten steel, and then adding alloy into the molten steel according to design components in the tapping process to obtain primary molten steel; and (3) refining: adding a refining slag charge into the primary molten steel, refining, feeding a sulfur wire at the later stage of refining, and then blowing argon and stirring until the mixture is uniform to obtain refined molten steel; degassing: carrying out vacuum degassing treatment on the refined molten steel to obtain degassed molten steel; pouring: pouring the degassed molten steel to obtain a casting blank; rolling: and rolling the casting blank to obtain the steel. The invention changes the time for adding the sulfur wire into the refining process instead of the primary refining process, and realizes the aim that the S content in the prepared high-sulfur steel is more than or equal to 0.100 wt% through the synergistic action of all the steps and parameters.
Description
Technical Field
The invention belongs to the technical field of high-sulfur steel, and particularly relates to high-sulfur steel and a preparation method thereof.
Background
In the process of smelting pure steel, sulfur is a harmful element, and when the content of sulfur in steel is too high, hot brittleness is caused, hot processing of steel is difficult, and the mechanical property of steel is deteriorated. However, in some steel grades requiring precise cutting, sulfur can improve the cutting performance of the steel grades, reduce the abrasion of a cutter, reduce the roughness of the processed surface and prolong the service life of the cutter, and generally, the machinability of the steel is increased along with the increase of the sulfur content in the steel.
In the process control of the high-sulfur steel on sulfur, if the smelting process is completely adopted and the iron sulfide is added, the recovery rate of the sulfur is low (30 percent, the reaction is generated: S + CaO → CaS + O), and the added amount of the iron sulfide is large, so that the purity of the molten steel is low, thereby increasing the production cost and reducing the market competitiveness.
Therefore, a method for preparing high-sulfur steel with low cost, simple operation and high S increasing efficiency is urgently needed.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide high-sulfur steel and a preparation method thereof, wherein the S content in the high-sulfur steel can be controlled under the condition of low cost.
The technical scheme adopted by the invention for solving the technical problem is as follows:
alloy components are added in the primary smelting furnace tapping process, but sulfur-containing alloy components are not added, appropriate slag charge is added, then deoxidation refining is carried out, a sulfur wire is fed in the later stage of the refining process, the sampling S is ensured to meet the requirement, and the molten steel is calcified and degassed in vacuum, so that the castability of the molten steel is improved.
And (3) normally smelting in the primary smelting furnace, adding ferromanganese, ferrosilicon and other alloys into the steel discharged from the primary smelting furnace, deoxidizing, adjusting and dividing the molten steel when the molten steel reaches the refining furnace, sampling and analyzing components except sulfur to meet standard requirements, calculating and feeding a sulfur line according to the amount of the molten steel in the later refining stage, blowing argon into the refining furnace to stir the components uniformly, and enabling the sampled components to meet the requirements until the refining is finished.
A high-sulfur steel (preparation method, comprising:
primary refining: carrying out primary smelting treatment on smelting raw materials to obtain molten steel, and then adding alloy into the molten steel according to design components in the tapping process to obtain primary molten steel;
and (3) refining: adding a refining slag charge into the primary molten steel, refining, feeding a sulfur wire at the later stage of refining, and then blowing argon and stirring until the mixture is uniform to obtain refined molten steel;
degassing: carrying out vacuum degassing treatment on the refined molten steel to obtain degassed molten steel;
pouring: and pouring the degassed molten steel to obtain a high-sulfur steel casting blank.
In the above method of producing a high-sulfur steel, as a preferred embodiment, the content of S in the high-sulfur steel is 0.090 to 0.130 wt%; preferably, the high-sulfur steel is medium-carbon high-sulfur steel.
In the above-described method for producing a high-sulfur steel, as a preferred embodiment, the alloy does not include a ferrosulfur alloy; more preferably, the alloys include ferrosilicon and ferromanganese.
In the above method for producing high-sulfur steel, as a preferred embodiment, carbon powder is added to the molten steel during the tapping process to adjust the C content therein; preferably, the content of C in the primary steelmaking water is 0.10-0.30%; preferably, the S content in the primary steelmaking water is 0.02-0.04%.
In the above method for producing high-sulfur steel, as a preferred embodiment, in the primary smelting step, the smelting raw materials are molten iron and scrap steel, and the temperature of the primary smelting treatment is 1600-; the primary refining time is 40-100min, preferably 60 min.
In the above-described method for producing high-sulfur steel, as a preferred embodiment, in the preliminary smelting step, both the preliminary smelting treatment and the tapping process are performed under argon blowing stirring to make the composition uniform; (ii) a More preferably, the flow rate of argon in the argon blowing stirring is 50-150m3H, further preferably, the flow rate of the argon gas is 100m3/h。
In the above method for producing a high-sulfur steel, as a preferred embodiment, in the refining step, the refining treatment includes: deoxidizing the molten steel, adjusting components to enable the components except sulfur to meet component design requirements during sampling analysis, then, calculating and feeding a sulfur line according to the molten steel amount and the S component design requirements in the later period of refining to enable the sulfur content in the molten steel to meet the design requirements, and then, carrying out calcification treatment on the molten steel until the refining is finished;
preferably, argon is blown and stirred all the time during the refining process to ensure that the components are uniform, and the flow rate of the argon is 70-100m3H, preferably 90m3/h；
Preferably, the argon is continuously blown after the sulfur line is fed and the stirring is carried out for 3 to 8min, preferably 5 min.
Preferably, the deoxidation is carried out by feeding aluminium wire and/or silicon carbide into the molten steel, wherein the quantity of aluminium wire used for refining is 0.5-2.0 Kg/ton steel, preferably 1.0 Kg/ton steel, and the quantity of silicon carbide is 1.0-2.0 Kg/ton steel, preferably 1.3 Kg/ton steel;
preferably, the calcification treatment is to feed a calcium silicate line into the molten steel, and preferably, the calcium silicate line is 100-150 m/furnace, preferably 120 m/furnace; preferably, the calcium silicon wire is 0.4 to 0.7Kg per ton of steel, preferably 0.5Kg per ton of steel.
In the above method for producing a high-sulfur steel, as a preferred embodiment, in the refining step, the time of the refining treatment is 30 to 60min, preferably 50 min. The inclusions of molten steel increase when the refining time is too long.
In the preparation method of the high-sulfur steel, as a preferred embodiment, in the refining step, the temperature of the refining treatment is 1400-1700 ℃, preferably 1550-1580 ℃; the refining treatment time is 30-60min, preferably 50min, refractory brick penetration and ladle accidents can occur if the temperature is too high and the refining time is too long, and molten steel inclusions with uneven components can be increased if the refining time is too short and the temperature is too low.
In the above-described method for producing high-sulfur steel, as a preferred embodiment, in the refining step, the refining slag is a mixture of lime and premelted slag, and the premelted slag includes 50% Al by mass2O3And 50% CaO, wherein CaO in the slag reacts with the molten steel S about 20min before refining until the chemical reaction is balanced. Preferably, the lime is 8-12Kg/t steel, preferably 10Kg/t steel, the pre-melted slag is 3-7Kg/t steel, preferably 5Kg/t steel, if the proportion is too high (i.e. the proportion of lime in the refined slag is too high), molten steel inclusions are not easy to remove, and if the proportion is too low (i.e. the proportion of lime in the refined slag is too low), the temperature rise in the refining process is slow, and the refined slag is added in the refining step to adsorb the inclusions in the molten steel.
In the above method for producing high-sulfur steel, as a preferred embodiment, in the refining step, the mass ratio of the refining slag to the primary molten steel is 10-15: 1000.
In the above method for producing high-sulfur steel, as a preferred embodiment, in the refining step, the refining treatment and the stirring process are performed under a protective atmosphere, which is argon.
In the above method for producing a high-sulfur steel, as a preferred embodiment, in the degassing step, the degree of vacuum of the vacuum degassing treatment is 60 to 100Pa, preferably 85Pa, for 20 to 30min, preferably 25 min.
In the above method for preparing high-sulfur steel, as a preferred embodiment, in the casting step, the temperature of the casting treatment is 1500-.
In the above method for producing high-sulfur steel, the obtained high-sulfur steel billet may be subsequently subjected to a deformation treatment by a method conventional in the art to obtain a high-sulfur steel workpiece of a desired shape and structure, and as a preferred embodiment, the method further comprises a rolling step of: and rolling the high-sulfur steel casting blank to obtain the high-sulfur steel.
A high-sulfur steel obtained by the preparation method of the high-sulfur steel.
Compared with the prior art, the invention has the following positive effects:
1. the invention provides a preparation method of high-sulfur steel, which solves the problems that S in a high-sulfur steel product has large fluctuation due to overhigh sulfur content, the S needs to be adjusted for many times and the purity of molten steel is poor under the condition of not increasing smelting cost. One of the invention points in the technical scheme of the invention is that when the steel is smelted and tapped from the primary smelting furnace, alloy components are added according to the weight of tapping molten steel, but iron sulfide alloy is not added, and sulfur components are controlled to be placed in a refining process. If the sulfur content is controlled by adding iron sulfide during tapping, the uniform time of the components entering molten steel is influenced due to the low density of the iron sulfide, and the low purity of the molten steel is also influenced due to the large addition amount of the iron sulfide.
2. After molten steel reaches a refining furnace, aluminum wires are fed for deoxidation and reaction with slag charge in the process of power transmission refining. Sampling and analyzing the components of the molten steel to meet the standard requirements, feeding a sulfur wire, stirring the molten steel, sampling and analyzing to obtain the components meeting the standard requirements.
3. After the molten steel is subjected to vacuum treatment, the sampling S meets the standard requirement, so the consumption of the alloy cannot be increased, and the sampling of the continuous casting molten steel is qualified.
4. The invention changes the time of adding the sulfur wire into the refining process instead of the primary refining process by 1), 2) slag is used for slagging in the refining process to absorb impurities so as to ensure the purity of molten steel, 3) argon is blown in the primary refining and the refining process, the control of a plurality of key nodes is realized, and the aim that the S content in the prepared high-sulfur steel is more than or equal to 1.00 wt% is realized by the synergistic action of all steps and parameters.
5. The method is simple and easy to operate, iron sulfide does not need to be added before refining treatment for sulfur increasing treatment, sulfur does not need to be added in the vacuum degassing and pouring processes, if the ferro-sulphur alloy is added in the refining process, the ferro-sulphur alloy and CaO used for refining generate CaS, the recovery rate is low, waste is caused, and the sulfur feeding wire can reach the qualified sulfur. The invention can obtain the sulfur-containing steel with the S content of more than 0.100 wt%.
Detailed Description
In order to highlight the objects, technical solutions and advantages of the present invention, the present invention is further illustrated by the following examples, which are presented by way of illustration of the present invention and are not intended to limit the present invention. The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The invention provides a preparation method of high-sulfur steel, which comprises the following steps:
primary smelting: carrying out primary smelting treatment on smelting raw materials in an electric furnace or a converter, wherein the smelting time is 40-100min, preferably 60min, the temperature is 1600-1700 ℃, and preferably 1640-1680 ℃; the whole process of tapping in the primary smelting treatment is blown inArgon gas with a flow rate of 50-150m3H, preferably 100m3H, stirring; when tapping in the primary smelting process, adding alloy according to design components into molten steel in the tapping process, adding carbon powder into the molten steel to adjust the content of C in the molten steel to obtain primary smelting molten steel, and adding refined slag charge into the primary smelting molten steel.
By analyzing and sampling, the S content in the primary steelmaking water is generally less than or equal to 0.040% (preferably 0.030%, namely the content of the end point S of the electric furnace/converter is less than or equal to 0.030 wt%) and does not meet the requirement of high-sulfur steel sulfur content design.
The preparation method of the application, if the preparation of the high-sulfur steel with the sulfur content of more than 0.100 wt% is realized, at least all required alloys need to be added in the tapping process of the primary smelting treatment, so that the alloy addition is reduced in the refining process.
Feeding a certain amount of sulfur wires through a wire feeding machine after the refined molten steel is qualified, blowing argon gas and stirring uniformly for 5 minutes, sampling and inspecting, wherein the sulfur content of the molten steel reaches 1.00%.
The argon is blown and stirred during the initial smelting tapping, impurities float upwards through stirring and are absorbed by white slag, the reaction time is short, and the sulfur recovery rate is improved.
Argon is blown into the refining treatment in the whole course, and the flow rate is 80-100m3H, preferably 90m3/h。
And degassing, pouring and rolling after refining to obtain the high-sulfur steel.
Example 1
This example is a method for the production of high-sulfur steel (mainly for large textile cylinders or free-cutting non-quenched and tempered work pieces).
The free-cutting steel is alloy steel which is added with a certain amount of one or more free-cutting elements such as sulfur, phosphorus, lead, calcium, selenium, tellurium and the like to improve the machinability. With the automation, high speed and precision of cutting, it is very important to require a steel material having good free-cutting properties, and such a steel is mainly used for machining on automatic cutting machines.
The process flow of the embodiment is as follows: electric furnace (molten iron and scrap steel), refining furnace-VD furnace-casting-rolling.
A preparation method of high-sulfur steel comprises the following steps:
(1) primary smelting: carrying out primary smelting treatment on smelting raw materials (30 tons of molten iron and 50 tons of scrap steel) in an electric furnace, wherein the smelting (primary smelting) time is 60min, and the temperature is 1640-; the whole primary refining process is 100m3Blowing argon gas at a flow rate of/h and stirring;
during tapping, ferrosilicon and ferromanganese are added at one time according to the component design requirements (see table 1 below) to obtain 70t of primary molten steel; adding refined slag (lime and premelted slag (including Al) with the mass ratio of 2: 1) into the primary molten steel2O350 percent of CaO and 50 percent of CaO), the mass ratio of the refining slag charge to the primary molten steel is 12: 1000.
the design components of the high-sulfur steel in percentage by mass (wt%) are shown in the following table 1:
TABLE 1
| C | Si | Mn | P | S | Cr | Ni | Mo | Cu | Al | |
| Lower limit of | 0.42 | 0.15 | 0.50 | 0 | 0.090 | 0 | 0 | 0 | 0 | 0 |
| Upper limit of | 0.50 | 0.35 | 0.80 | 0.025 | 0.130 | 0.30 | 0.25 | 0.20 | 0.30 | 0.050 |
(2) Refining: and refining the primary molten steel added with the refining slag charge in a refining furnace, feeding an aluminum wire for deoxidation in the power-on refining process, feeding a sulfur wire after sampling detection is qualified, blowing argon for stirring uniformly for 5 minutes, and obtaining the refined molten steel after sampling detection is qualified (the content of each component is shown in the following table 2). 90m in the refining process3Blowing argon at the flow rate of/h, wherein the refining treatment temperature is 1550-;
the actual composition of the above high sulfur steel in percent by mass (wt%) is as follows:
TABLE 2
| C | Si | Mn | P | S | Cr | Ni | Mo | Cu | Al | |
| Lower limit of | 0.45 | 0.20 | 0.65 | 0 | 0.100 | 0.05 | 0.05 | 0.05 | 0.05 | 0.010 |
| Upper limit of | 0.48 | 0.25 | 0.70 | 0.015 | 0.120 | 0.20 | 0.20 | 0.20 | 0.20 | 0.025 |
The mass percentage of S in the refined molten steel is 0.100 wt%.
(3) Degassing: and (3) carrying out vacuum degassing treatment on the refined molten steel in a VD furnace, wherein the vacuum degree is less than or equal to 85Pa, and the time is 25min, so as to obtain degassed molten steel.
(4) Pouring: pouring the degassed molten steel at the temperature of 1500-.
(5) Rolling: and (4) sending the casting blank to a steel mill for rolling treatment to obtain steel.
The floating time of the impurities such as CaS is gathered, the floating time of the impurities is longer when a sulfur line is fed in refining than when the sulfur line is fed in vacuum, the generated sulfide impurities are less, and during continuous casting production, the CaS which is gathered on the inner wall of a continuous casting nozzle is less and accounts for 10 percent, and the length of the CaS is 20 micrometers.
Comparative example 1 sulfur line feed during vacuum treatment
The sulfur wire is fed in a vacuum treatment step (instead of being fed in the later refining stage in the application), the products are CaS and MgO. Al2O3, the impurities are gathered and do not float upwards, during continuous casting production, the CaS is attached to the inner wall of a continuous casting nozzle, the aperture of the nozzle is smaller and smaller, and meanwhile, the impurities exist in steel inspection, the content of the CaS reaches 30%, and the length is 50 microns.
Comparative example 2
The S is controlled by adding iron sulfide in the smelting process (the other steps are the same as the step in the embodiment 1), and because the recovery rate is only 15 percent, the adding amount is increased, the oxide inclusions brought by the iron sulfide are increased, and the MgO. Al2O3 is increased to reach 20 percent, and the length is 60 microns.
The influence of the sulfur line control S in the later refining period of example 1 and the control S in the comparative example 2 (the control S by adding the iron sulfide alloy) on the number and the quality of the continuous casting furnaces is shown in the following table 1.
TABLE 1
| Number of continuous casting furnaces | Results | S recovery rate | |
| Example 1 | 6 | The water gap can be normally and continuously cast | 40％ |
| Comparative example 1 | 4 | Continuous casting nozzle plug | 40％ |
| Comparative example 2 | 4 | Continuous casting nozzle plug | 15％ |
The influence of the sulfur feeding line S in the later period of refining in the example 1 and the comparative example 2 (the control of S by adding the iron sulfide alloy) on the quality of sulfide is as follows:
comparative example 2 control of S with iron sulfide alloy, where the sulfide obtained is shown in fig. 1, and it can be seen that the sulfide is in the form of long stripes and is unevenly distributed.
In contrast, in example 1 of the present application, the control of sulfur feeding line S in the late stage of refining is shown in FIG. 2, and the resulting sulfides are seen to be in the form of a spindle and uniformly distributed.
Claims (10)
1. A method for producing high-sulfur steel, characterized by comprising:
primary refining: carrying out primary smelting treatment on smelting raw materials to obtain molten steel, and then adding alloy into the molten steel according to design components in the tapping process to obtain primary molten steel;
and (3) refining: adding a refining slag charge into the primary molten steel, refining, feeding a sulfur wire at the later stage of refining, and then blowing argon and stirring until the mixture is uniform to obtain refined molten steel;
degassing: carrying out vacuum degassing treatment on the refined molten steel to obtain degassed molten steel;
pouring: and pouring the degassed molten steel to obtain a high-sulfur steel casting blank.
2. The method of producing a high-sulfur steel as claimed in claim 1, wherein the content of S in the high-sulfur steel is 0.090-0.13 wt%; preferably, the high-sulfur steel is medium-carbon high-sulfur steel.
3. The method of producing a high-sulfur steel according to claim 1, wherein the alloy does not include a ferrosulfur alloy; more preferably, the alloys include ferrosilicon and ferromanganese;
preferably, carbon powder is added into the molten steel during the tapping process to adjust the content of C in the molten steel; preferably, the content of C in the primary steelmaking water is 0.10-0.30%;
preferably, the S content in the primary steelmaking water is 0.02-0.04%.
4. The method for preparing high-sulfur steel as claimed in claim 1, wherein in the primary smelting step, the smelting raw materials are molten iron and scrap steel, the primary smelting treatment temperature is 1600-1700 ℃, and the primary smelting treatment time is 40-100 min;
preferably, in the primary smelting step, the primary smelting treatment and the tapping process are both carried out under argon blowing stirring; more preferably, the flow rate of argon in the argon blowing stirring is 50-150m3H, further preferably, the flow rate of the argon gas is 100m3/h。
5. The method of producing high-sulfur steel according to claim 1, wherein in the refining step, the refining treatment includes: deoxidizing the molten steel, adjusting components to enable the components except sulfur to meet component design requirements during sampling analysis, then, calculating and feeding a sulfur line according to the molten steel amount and the S component design requirements in the later period of refining to enable the sulfur content in the molten steel to meet the design requirements, and then, carrying out calcification treatment on the molten steel until the refining is finished;
preferably, argon is blown and stirred all the time during the refining process to ensure that the components are uniform, and the flow rate of the argon is 70-100m3H, preferably 90m3/h；
Preferably, after feeding a sulfur line, continuously blowing argon gas and stirring for 3-8min, preferably 5 min;
preferably, the deoxidation is carried out by feeding aluminium wire and/or silicon carbide to the molten steel, wherein the quantity of aluminium wire is 0.5-2.0 Kg/ton steel, preferably 1.0 Kg/ton steel, and the quantity of silicon carbide is 1.0-2.0 Kg/ton steel, preferably 1.3 Kg/ton steel;
preferably, the calcification treatment is to feed a calcium silicate line into the molten steel, and preferably, the calcium silicate line is 100-150 m/furnace, preferably 120 m/furnace; preferably, the calcium silicon wire is 0.4 to 0.7Kg per ton of steel, preferably 0.5Kg per ton of steel.
6. The method for producing a high-sulfur steel according to claim 1, wherein in the refining step, the time of the refining treatment is 30 to 60min, preferably 50 min;
preferably, the temperature of the refining treatment is 1400-1700 ℃, preferably 1550-1580 ℃.
7. Method for producing a high-sulfur steel according to claim 1, wherein, in the refining step, the refining slag is a mixture of lime and premelted slag, the premelted slag comprising 50% Al by mass2O3And 50% CaO;
preferably, the lime is 8-12Kg/t steel, preferably 10Kg/t steel; the pre-melted slag is 3-7Kg/t steel, preferably 5Kg/t steel.
8. The method for producing high-sulfur steel according to claim 1, wherein in the refining step, the mass ratio of the refining slag to the primary molten steel is 10-15: 1000;
preferably, in the refining step, the refining treatment and the stirring process are both performed under a protective atmosphere, preferably argon.
9. The method for producing a high-sulfur steel according to claim 1, wherein, in the degassing step, the vacuum degree of the vacuum degassing treatment is 60 to 100Pa, preferably 85 Pa; the vacuum degassing treatment time is 20-30min, preferably 25 min;
preferably, in the pouring step, the temperature of the pouring treatment is 1500-; the casting speed is 0.30-0.40m/min, preferably 0.36 m/min;
preferably, the preparation method further comprises: rolling: and rolling the high flow steel casting blank to obtain the high-sulfur steel.
10. A high-sulfur steel produced by the method for producing a high-sulfur steel according to any one of claims 1 to 9.
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| CN202010917127.5A CN111945056A (en) | 2020-09-03 | 2020-09-03 | High-sulfur steel and preparation method thereof |
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| CN113201620A (en) * | 2021-05-19 | 2021-08-03 | 宝武集团鄂城钢铁有限公司 | Method for smelting sulfur-containing steel grade by using desulphurization slag |
| CN113430449A (en) * | 2021-06-24 | 2021-09-24 | 河南中原特钢装备制造有限公司 | Smelting and continuous casting production process of sulfur-containing free-cutting steel ASTM1141 |
| CN113584411A (en) * | 2021-07-30 | 2021-11-02 | 大冶特殊钢有限公司 | Sulfur-containing ferritic stainless steel and manufacturing method thereof |
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