METHOD FOR MANUFACTURING STAINLESS STEEL |
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申请号 | EP12762777.6 | 申请日 | 2012-03-06 | 公开(公告)号 | EP2692873A1 | 公开(公告)日 | 2014-02-05 |
申请人 | Nisshin Steel Co., Ltd.; | 发明人 | SUGIURA, Masayuki; NAKAGAWA, Tomoki; | ||||
摘要 | A method for manufacturing stainless steel according to the present invention includes the steps of: generating hot metal 2 through melting in a melting furnace 1 a starting material for making stainless steel; generating crude stainless molten steel 2a through decarburization of the hot metal 2 in a refining furnace 4; adding calcium carbonate 11 to slag 10 that is generated in the crude stainless molten steel 2a through the decarburization, without addition of a reducing agent, to solidify the slag 10; separating the solidified slag 10; and returning the separated slag 10 to the melting furnace 1. | ||||||
权利要求 | |||||||
说明书全文 | The present invention relates to a method for manufacturing stainless steel. In the manufacturing process of stainless steel, hot metal is produced through melting of starting materials, the produced hot metal is refined into molten steel such as through decarburization, in which carbon that lowers the strength of stainless steel is removed from the produced hot metal, and then a tabular slab is produced through casting of the molten steel. Slag is generated out of the hot metal during the decarburization. The generated slag is made to solidify and is removed from the molten steel, before casting, because slag adversely affects the quality of stainless steel products. The removed slag contains components of valuable metals such as oxides of chromium (Cr), which may be constituent components of stainless steel. Attempts have accordingly been made to reuse the valuable metals in slag. For instance, slag solidification is accomplished through addition of calcium oxide (CaO) to slag in molten steel at the terminal phase of a decarburization process, as disclosed in Patent Document 1. Ordinarily, reducing agents such as silicon (Si) and aluminum alloy are added to slag, before addition of calcium oxide, in order to recover chromium through reduction of chromium oxides contained in the slag. Patent Document 2 discloses a technique where solidified slag after being removed from molten steel is returned to a furnace (melting furnace) for generating hot metal from starting materials for making stainless steel and then the slag is melted together with the starting materials for making stainless steel, and as a result, valuable metals contained in the slag are reused as stainless steel starting materials.
In the slag solidification technique disclosed in Patent Document 1, however, the additive amount of calcium oxide is substantial, and hence the amount of slag after solidification is likewise significant. In the technique disclosed in Patent Document 2, returning large amounts of slag to a melting furnace entails also returning significant amounts of impurities contained in the slag, which cannot be used for steelmaking. This lowers the production efficiency of stainless steel from the hot metal that is generated in the melting furnace, and, as a consequence, the amount of slag that can be returned to the melting furnace is limited. The excess slag that cannot be returned to the melting furnace increases in a case where slag solidified according to the solidification technique disclosed in Patent Document 1 is to be returned to the melting furnace in accordance with the technique disclosed in Patent Document 2. This excess slag must be disposed of after recovery, by some other means, of the valuable metals contained in the slag. This is problematic in that, as a result, costs increase as the amount of excess slag increases. It is an object of the present invention, in order to solve the above problem, to provide a method for manufacturing stainless steel aimed at reducing the amount of slag that is to be disposed of. In order to solve the above problem, the method for manufacturing stainless steel according to the present invention includes the steps of: generating hot metal through melting in a melting furnace a starting material for making stainless steel; generating chromium-containing molten steel through decarburization of the hot metal in a refining furnace; adding calcium carbonate to slag that is generated in the chromium-containing molten steel through the decarburization, without addition of a reducing agent, to solidify the slag; separating the solidified slag; and returning the separated slag to the melting furnace. The method for manufacturing stainless steel according to the present invention allows reducing the amount of slag that is to be disposed of.
A method for manufacturing stainless steel in an embodiment of the present invention will be explained next with reference to the accompanying drawings. With reference to In the steelmaking process (A), a starting material for making stainless steel is melted in an electric furnace 1, to generate hot metal 2, and the generated hot metal 2 is charged into a converter 4 by way of a hot metal ladle 3. Here, the electric furnace 1 constitutes a melting furnace. In the primary refining process (B), oxygen is blown into the converter 4 via a nozzle 4a, to perform thereby crude decarburization by removing carbon contained in the hot metal 2. Crude stainless molten steel 2a (see Here, the converter 4 constitutes a refining furnace. In the secondary refining process (C), the crude stainless molten steel 2a is introduced, together with the ladle 5, into a vacuum degasser (VOD) 6, where finish-decarburization is performed. Pure stainless molten steel is generated through finish-decarburization of the crude stainless molten steel 2a. In the casting-rolling process (D), the ladle 5 is removed from the vacuum degasser 6 and is set in a continuous casting apparatus (CC) 7. The stainless molten steel is poured into a mold of the continuous casting apparatus 7, and a tabular stainless steel slab 8 is formed as a result. The formed slab 8 is hot-rolled or cold-rolled to yield hot-rolled or cold-rolled steel strip. With reference to First, in a hot metal pouring process (B1), the hot metal 2 generated in the electric furnace 1 (see Here, the crude stainless molten steel 2a constitutes chromium-containing molten steel. Once the decarburization of the hot metal 2 is over, calcium carbonate (CaCO3) 11 at ordinary temperatures, which is a solidification material, is added to the slag 10 on the surface of the crude stainless molten steel 2a, in a solidification material input process (B3). The calcium carbonate 11 is added in the form of lump-like calcium carbonate having a granularity range of from 10 mm to 50 mm. The calcium carbonate 11 absorbs heat from the slag 10 to heat up to the decomposition temperature. The calcium carbonate 11 then undergoes thermal decomposition into calcium oxide (CaO) in solid form and gaseous carbon dioxide (CO2), as indicated in Formula 1 below. CaCO3 (solid) → CaO (solid) + CO2 (gas) (Formula 1) Calcium carbonate absorbs 178.39 kilojoules of heat per mole (molar mass 100.087 g) (178.39 kJ/mol) in the thermal decomposition reaction of Formula 1. In the thermal decomposition reaction of Formula 1, 100 kg of calcium carbonate decomposes into about 56 kg of calcium oxide and about 44 kg of carbon dioxide. The slag 10 is cooled as a result of the endothermic reaction of the calcium carbonate 11, and solidifies in a state where the slag 10 contains calcium oxide that is formed from the calcium carbonate 11. The amount of heat absorbed from the slag 10 is herein 2708 kilojoules per kg of calcium carbonate. If calcium oxide at ordinary temperatures is used as the solidification material of the slag 10, the amount of heat absorbed from the slag 10 is 1125 kilojoules per kg of calcium oxide. That is, the endothermic capacity per kg of calcium carbonate, when the latter is used in slag solidification, is about 2.4 times the endothermic capacity per kg of calcium oxide. In a tapping process (B4) after the solidification material input process (B3), the converter 4 is tilted and the crude stainless molten steel 2a alone is tapped into the ladle 5 via a tap hole 4b of the converter 4. The ladle 5 with the tapped crude stainless molten steel 2a moves onto the secondary refining process (C) of The converter 4, out of which the crude stainless molten steel 2a is tapped in the tapping process (B4), is returned from the tilted state to the original state in a subsequent tilt return process (B5), and is then tilted again in a slag removal process (B6), whereupon the solidified slag 10 inside the converter 4 is discharged into a vessel 12, via an opening 4c at the top, i.e. the slag is removed. The removed slag 10 is returned to the electric furnace 1 (see The rationale for prescribing a granularity range of 10 mm to 50 mm for the calcium carbonate 11 that is added to the slag 10 of the crude stainless molten steel 2a in the solidification material input process (B3) is as follows. First, if the granularity of the calcium carbonate 11 is larger than 50 mm, the surface area ratio (calcium carbonate surface area/slag surface area), which is the ratio of the surface area of the calcium carbonate 11 with respect to the surface area of the slag 10, is too small and accordingly, the mutual contact surface area becomes smaller, and the calcium carbonate 11 absorbs less heat from the slag 10. As a result, the reaction time between the calcium carbonate 11 and the slag 10, i.e. the time required for solidification of the slag 10, becomes longer, and stainless steel productivity decreases. If the granularity of the calcium carbonate 11 is smaller than 10 mm, the surface area ratio (calcium carbonate surface area/slag surface area) is too large, and hence it becomes possible to shorten the reaction time between the calcium carbonate 11 and the slag 10. In this case, however, the granularity of the calcium carbonate 11 is excessively small, and hence the calcium carbonate 11 just stays at the surface of the slag 10 and fails to react sufficiently with the latter, and/or the updraft of carbon dioxide that is generated out of the calcium carbonate 11 through thermal decomposition drives the calcium carbonate 11 out of the converter 4, so that, as a result, the slag 10 fails to be sufficiently cooled and solidified. According to According to In the electric furnace 1 (see As described above, the method for manufacturing stainless steel according to the present invention includes the steps of: generating hot metal 2 through melting of a starting material for making stainless steel, in the electric furnace 1; generating crude stainless molten steel 2a through decarburization of the hot metal 2 in the converter 4; adding calcium carbonate 11 to slag 10 that is generated in the crude stainless molten steel 2a through decarburization, without addition of a reducing agent, to solidify the slag 10; separating the solidified slag 10; and returning the separated slag 10 to the electric furnace 1. The calcium carbonate 11 has higher cooling capability than calcium oxide or the like, and can cool and solidify the slag 10 in smaller amounts. Therefore, this allows a reduction in the amount of slag 10 that is generated after solidification. By returning the slag 10 after solidification to the electric furnace 1, without reduction through addition of a reducing agent, the melting heat in the electric furnace 1 can be exploited by the chromium oxides contained in the slag 10 to be reduced to chromium through reaction with carbon or silicon contained in the starting materials for making stainless steel, so that the chromium is reused as a stainless steel starting material. This allows the suppression of increases in the amount of slag 10 that is generated due to a reducing agent. Further, by returning the slag 10 after solidification to the electric furnace 1 and reusing the slag 10 as a stainless steel starting material, the amount of slag 10, which requires a separate recovery process for chromium that is a valuable metal and is to be disposed of after the recovery, can be reduced. Accordingly, the amount of slag 10, from which valuable metals are recovered in a separate process, and which is to be disposed of, can be lowered by reducing the generation amount of slag 10 after solidification and reusing the slag 10 after solidification for the production of stainless steel. As a result of the above, it becomes possible to reduce the recovery cost of valuable metals from the slag 10, and to reduce the disposal cost of the slag 10 after recovery. The amount of slag 10 that is returned to the electric furnace 1 can be lowered by reducing the amount of slag 10 after solidification. In turn, this allows an increase in the charging amount of starting material for making stainless steel into the electric furnace 1 and, thereby, increasing the amount of stainless steel that is produced per steelmaking charge, while reducing production costs. Costs can also be reduced by returning the slag 10 after solidification to the electric furnace 1, so no process need be carried out in order to melt the slag 10. The slag 10 that is generated in the converter 4 contains chromium oxide (Cr2O3) of a high melting point, as one chromium oxide. In a case where the chromium oxide is reduced in the converter 4 in order to recover chromium, the slag 10 requires the use of a reducing agent containing silicon such as ferrosilicon, etc. This entails higher costs. By contrast, as, in the electric furnace 1, carbon or silicon contained in the ferrochromium or ferronickel in the starting material for making stainless steel can be exploited as reducing agents, it becomes possible to lower the cost of recovering valuable metals from the slag 10. If the chromium oxide is reduced in the converter 4, a reducing agent such as ferrosilicon is charged when the crude stainless molten steel 2a is in a state after decarburization and at high temperature (about 1700 to about 1800°C). The basicity in the slag 10 (calcium oxide content/silicon dioxide content) drops as a result. Low basicity translates into increased solubility of magnesium oxide (MgO), which is a constituent component of the furnace body of the converter 4, to elute the magnesium oxide so that the durability of the converter 4 is lessened. By contrast, as the temperature of the hot metal 2 that is generated in the electric furnace 1 is comparatively low, of up to about 1600°C, drops in the basicity in the slag 10 that is returned to the electric furnace 1 are suppressed, and therefore, loss of durability of the furnace body of the electric furnace 1 is likewise suppressed. The calcium carbonate takes the form of lumps having a granularity range from 10 mm to 50 mm. As a result, the contact surface area between the added calcium carbonate 11 and the slag 10 is secured and the calcium carbonate 11 can reach the interior of the slag 10, and therefore, the added calcium carbonate 11 can sufficiently cool and solidify the entirety of the slag 10. |