WO2017159840A1 - Molten-iron pretreatment method - Google Patents
Molten-iron pretreatment method Download PDFInfo
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- WO2017159840A1 WO2017159840A1 PCT/JP2017/010850 JP2017010850W WO2017159840A1 WO 2017159840 A1 WO2017159840 A1 WO 2017159840A1 JP 2017010850 W JP2017010850 W JP 2017010850W WO 2017159840 A1 WO2017159840 A1 WO 2017159840A1
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- mass
- slag
- hot metal
- converter slag
- converter
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002203 pretreatment Methods 0.000 title claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 13
- 239000002893 slag Substances 0.000 claims abstract description 185
- 238000007670 refining Methods 0.000 claims abstract description 68
- 239000002245 particle Substances 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims description 83
- 239000002184 metal Substances 0.000 claims description 83
- 238000000034 method Methods 0.000 claims description 43
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 39
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000004513 sizing Methods 0.000 claims description 7
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 78
- 239000000292 calcium oxide Substances 0.000 description 39
- 235000012255 calcium oxide Nutrition 0.000 description 39
- 230000012447 hatching Effects 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 14
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 238000009628 steelmaking Methods 0.000 description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000005261 decarburization Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/02—Dephosphorising or desulfurising
-
- 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
-
- 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
Definitions
- the present invention relates to a hot metal preliminary treatment method.
- This application claims priority based on Japanese Patent Application No. 2016-053234 for which it applied to Japan on March 17, 2016, and uses the content here.
- a hot metal pretreatment (de-P or de-S) is performed using a refining agent (dephosphorization agent or desulfurization agent) containing CaO as an essential component.
- a refining agent dephosphorization agent or desulfurization agent
- CaO as an essential component.
- the melting point of CaO is as high as 2625 ° C.
- the method of pulverizing CaO to promote reaction hatching in molten steel, or adding CaF 2 , Al 2 O 3 or MgO to lower the melting point The technique of reducing and promoting reaction of slag and molten iron is widely adopted.
- converter slag generated in the converter refining (de-C) process following the hot metal pretreatment process is a technology for recycling slag generated in the steelmaking process (hot metal pretreatment process-converter refining process-secondary refining process).
- hot metal pretreatment process-converter refining process-secondary refining process After cooling, pulverizing and increasing the hatching speed, and then using the technology used as a refining agent in the hot metal pretreatment process (Patent Document 1) and ladle slag generated in the secondary refining process
- Patent Document 2 used as is disclosed.
- the invention of Patent Document 1 was made by paying attention to the fact that the converter slag generated in the converter refining (de-C) process contains a lot of CaO and has a high basicity.
- the invention is significant in that it can reduce the amount of converter slag discharged by recycling.
- the converter slag alone has a hatching rate of only about 50%, so it is necessary to additionally use a large amount of quicklime (CaO not derived from converter slag).
- the effect of reducing the refining agent cost cannot be expected.
- Patent Document 2 is an invention made by paying attention to the fact that the ladle slag generated in the secondary refining process contains a large amount of Al 2 O 3 together with CaO.
- the slag formation promoting effect by Al 2 O 3 with an effect of lowering the melting point of the slag can enjoy simultaneously the viscosity of the slag increases.
- the viscosity of the slag is high, there is a problem that the slag tends to foam, and the risk of occurrence of slopping that hinders operation due to overflow of the slag from a reaction vessel such as a converter or torpedo car.
- the present invention has been made in view of the above circumstances, and aims to reduce the amount of slag discharged outside the system, avoid the occurrence of slopping, and reduce the amount of quicklime used as a refining agent.
- An object is to provide a hot metal preliminary treatment method.
- the hot metal preliminary treatment method is a hot metal preliminary treatment in which the converter slag obtained when refining the molten iron that has undergone the hot metal preliminary treatment step is recycled as a refining agent for hot metal pretreatment. It is a method, Comprising: The particle size of the said converter slag becomes the range of 3 mm or more and less than 25 mm, and the ratio of the converter slag whose particle size is 20 mm or more and less than 25 mm among the said converter slag is with respect to the whole quantity of the said converter slag.
- the hot metal preliminary treatment method having the above configuration, it is possible to reduce the amount of slag discharged from the system, avoid the occurrence of slopping, and reduce the amount of quicklime used as a refining agent.
- the converter slag is 100% by mass in the hot metal pretreatment container simultaneously with the third step.
- a sixth step of adding one or more of K 2 O, Li 2 O, Na 2 O, CaF 2 , MgO, and SrO to 0.3 mass% or more and less than 5.0 mass%, respectively. You may have.
- hatching of the converter slag can be promoted without increasing the viscosity of the slag in the hot metal pretreatment container. While aiming at reduction, generation
- the converter slag obtained when decarburizing and refining the hot metal that has undergone the hot metal pretreatment process is low in the concentration of P (phosphorus) and contains basic slag required for de-P and de-S (nitrogen). It contains a lot of CaO, which is the main component.
- the hot metal preliminary treatment, converter refining, and secondary refining of the blast furnace hot metal are sequentially performed.
- the converter slag obtained by the converter refining is recycled as a refining agent in the hot metal pretreatment step, whereby quick lime (converter slag) used as a refining agent in the hot metal pretreatment step.
- quick lime converter slag
- the amount of converter slag out of the system is reduced.
- the melting point of the converter slag is about 1400 ° C.
- the lump of the converter slag itself does not melt at the hot metal pretreatment temperature of about 1300 ° C. to 1350 ° C.
- Al 2 O 3 , MnO, FeO, K 2 O, Li 2 O, Na 2 O, CaF 2 , MgO, and SrO are used as substances that promote the low melting point of the converter slag.
- the particle size of the converter slag is reduced.
- the converter slag can be rapidly melted to improve the hatching rate, and the refining efficiency can be improved, that is, the amount of quick lime additionally used as a refining agent can be reduced and the P removal rate can be improved.
- the converter slag obtained at the time of converter refining (de-C) is discharged, cooled, and then sieved into fine particles to obtain a particle size (equivalent sphere diameter).
- the ratio of the converter slag having a particle size of 20 mm or more and less than 25 mm in the converter slag is 10% by mass or more and less than 15% by mass with respect to the total amount of the converter slag.
- the reaction interface area is increased and heat transfer is promoted, so that the converter slag can be rapidly melted.
- the particle size of the converter slag 3 mm or more, it is possible to suppress part or all of the converter slag introduced by dust collection from dissipating outside the reaction vessel, and to fully contribute to the reaction. it can. Therefore, the amount of quicklime used additionally can be suppressed.
- the particle size of the converter slag By setting the particle size of the converter slag to less than 25 mm, a large specific surface area of the converter slag can be secured, and the melting time of the slag can be shortened, so that the hatching rate increases. Since refining efficiency rises by this, the amount of quicklime used additionally can be controlled.
- the ratio of the converter slag having a particle size of 20 mm or more (and less than 25 mm) to the total amount of the converter slag is in the range indicated by the arrow in the graph, that is, the grains of the converter slag as described above.
- Al 2 O 3 of 1.0% by mass or more and less than 10.0% by mass is added to 100% by mass (total amount) of the converter slag in the hot metal pretreatment container.
- 0.3 mass % Or more and less than 10.0% by mass of MnO is added (fourth step).
- the addition amount of Al 2 O 3 is 1.0 mass% or more, the effect of lowering the melting point of the slag is sufficiently obtained, and the melting point of the slag becomes 1250 ° C. or less, which is the hot metal temperature, and the hatching rate is improved. As a result, the amount of quicklime used additionally can be suppressed.
- the addition amount of Al 2 O 3 is less than 10.0% by mass, an increase in slag viscosity is suppressed and foaming of slag is suppressed, so that the probability of occurrence of slopping in which slag overflows from the reaction vessel may be lowered. it can.
- the amount of MnO added is 0.3% by mass or more, an effect of suppressing an increase in slag viscosity can be obtained. As a result, the probability of occurrence of slopping can be reduced.
- the amount of MnO added is preferably within 10.0% by mass.
- the MnO source for example, a manganese ore pulverized to about 30 mm can be used.
- the fourth step of adding MnO may be performed simultaneously with the third step of adding Al 2 O 3 , before the third step, or after the third step.
- FIG. 3 As a result of the test experiment study. According to the results of FIG. 3, it can be seen that the hatching rate of the converter slag is high when the charging time of Al 2 O 3 introduced as the hatching accelerator is before or simultaneously with the converter slag injection ( The range indicated by the arrows in the graph). On the other hand, it was found that when Al 2 O 3 was introduced after the converter slag was introduced, the hatching promoting effect was low.
- secondary refining slag obtained when secondary refining of molten steel that has undergone a converter refining process.
- secondary refining slag contains about 20.0 mass% to 40.0 mass% of Al 2 O 3 . Therefore, if the chemical composition of the secondary refining slag is analyzed in advance to determine the input amount, the desired Al 2 O 3 concentration can be achieved only by the input of the secondary refining slag.
- the recycling of secondary smelting slag as an Al 2 O 3 source reduces the amount of slag generated in the steelmaking process (from the hot metal pretreatment process to the converter refining process to the secondary refining process). It is equivalent and can reduce the cost and environmental burden associated with slag disposal. That is, since the amount of secondary refining slag used matches the amount of emission reduction outside the slag system, the amount of secondary refining slag used can reduce the cost and environmental load associated with slag disposal.
- Al 2 O 3 -containing minerals such as bauxite and gibbsite, waste alumina bricks, and the like can be used.
- the above-mentioned FeO is used as a solid oxygen source during hot metal pretreatment. It is preferable to have a fifth step of charging 1.0% by mass or more and less than 20.0% by mass of iron oxide into the hot metal pretreatment vessel with respect to 100% by mass of the above converter slag. Thereby, the improvement of refining efficiency is realizable.
- the iron oxide source in addition to iron ore, powdered ore sintered into a lump, pellets formed from scale powder and dust, and the like can be used.
- the fifth step is preferably after the first step and before the second step, or at the same time as the second step.
- the above-mentioned K 2 O, Li 2 O, Na 2 O, CaF 2 , MgO, and SrO are used as hatching accelerators for reducing the melting point of slag.
- a first or two or more of these hatching accelerators are added in an amount of 0.3 to less than 5.0% by mass into the hot metal pretreatment vessel with respect to 100% by mass of the above converter slag. It is preferable to have six steps. Thereby, the hatching rate of converter slag can be increased and refinement efficiency can be improved.
- the refining efficiency is further improved.
- the input amount of the above hatching accelerator is less than 5.0% by mass, it is possible to suppress the production cost as well as the effect of improving the refining efficiency.
- the hatching promoting effect of converter slag can be enjoyed by adding these hatching accelerator components at the same timing as Al 2 O 3 .
- compounds containing the above components for example, K 2 CO 3 , Li 2 CO 3 , Na 2 CO 3 , MgCO 3 , SrCO Carbonate such as 3 , ores such as fluorite, feldspar, and dolomite, and those obtained by pulverizing minerals to about 20 mm can be suitably used.
- the method for charging the converter slag and the hatching accelerator such as Al 2 O 3 , MnO, FeO, K 2 O, Li 2 O, Na 2 O, CaF 2 , MgO, SrO, etc. is not particularly limited. It may be added to the hot metal pretreatment container at the time of pretreatment. In addition to an operation mode in which converter refining and hot metal pretreatment are performed in separate smelting vessels, it can be applied to an operation mode in which converter refining and hot metal pretreatment are alternately performed using the same converter.
- the hot metal preliminary treatment method recycles the converter slag obtained when the hot metal having undergone the hot metal pretreatment process is refined as a refining agent for hot metal pretreatment. It is.
- the particle size of the converter slag is in a range of 3 mm or more and less than 25 mm, and the ratio of the converter slag having a particle size of 20 mm or more and less than 25 mm among the converter slag is the converter. It has the 1st process of sizing the said converter slag so that it may become 10 to 15 mass% with respect to the whole quantity of slag.
- the hot metal pretreatment method according to the present embodiment includes a second step of charging the converter slag after sizing into a hot metal pretreatment container. Further, the hot metal preliminary treatment method according to the present embodiment is based on 100% by mass of the converter slag after the first step and before the second step, or simultaneously with the second step. There is a third step in which Al 2 O 3 of 1.0% by mass or more and less than 10.0% by mass is charged into the hot metal pretreatment container. Further, in the hot metal pretreatment method according to the present embodiment, MnO of 0.3% by mass or more and less than 10.0% by mass with respect to 100% by mass of the converter slag is introduced into the hot metal pretreatment container. It has the process of.
- the P removal rate must be 80% or more in order to satisfy the P concentration allowed for the product.
- the amount of additional quicklime in the decarburization furnace is adjusted in order to achieve a de-P ratio of 80% or more. In the case where the present invention is not carried out, the ratio of additional quicklime is 60 to 90%.
- the melting point of the converter slag was about 1400 ° C. when the present invention was not carried out. If the melting point of the converter slag is lowered to the hot metal temperature of 1350 ° C. or less, the hatching rate is improved and the refining efficiency can be improved.
- the basic unit for reducing slag out-of-system emissions is essentially the same as the basic unit for secondary slag slag input as an Al 2 O 3 source because secondary slag that should be discharged outside the system is recycled. .
- the hatching rate of converter slag is defined as (CaO concentration in slag after refining) / (CaO concentration when all converter slag is dissolved) ⁇ 100 (%), which is a value exceeding 40 (%) Then, it was judged that the amount of quicklime used as a refining material could be reduced, so that the refining efficiency could be improved.
- the ratio of the converter slag having a particle diameter of 3 mm or more and less than 25 mm and the converter slag having a particle diameter of 20 mm or more and less than 25 mm is 10 mass with respect to the total amount of the converter slag.
- the converter slag that has been sized so as to be not less than 15% and less than 15% by mass is composed of Al 2 O 3 of not less than 1.0% by mass and less than 10.0% by mass, and not less than 0.3% by mass and less than 10.0% by mass.
- Comparative Examples 30 and 31 in which the ratio of the particle size of 20 mm or more and less than 25 mm is as high as 17% by mass and 50% by mass, respectively, the hatching rate of the converter slag is low, and a large amount of quick lime is necessary to maintain the de-P rate. It was.
- Comparative Example 33 in which the amount of Al 2 O 3 added was as high as 20.0% by mass, significant slopping occurred because the viscosity of the slag increased, and the operation was hindered.
- the hot metal pretreatment method according to the present invention hatching of converter slag can be promoted without increasing the viscosity of the slag in the hot metal pretreatment container. Moreover, according to the hot metal pretreatment method according to the present invention, it is possible to avoid an operation hindering factor such as blocking of the charging hopper.
- the hot metal preliminary treatment method according to the present invention aims to reduce the out-of-system discharge of slag by reusing slag generated in the steelmaking process as a refining agent, avoiding the occurrence of slopping due to the use of the refining agent, and In the steelmaking process of high-purity steel, the amount of quicklime (CaO not derived from converter slag) used as a refining agent can be reduced, and the value in the industry is extremely high.
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Carbon Steel Or Casting Steel Manufacturing (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
Abstract
Description
本願は、2016年3月17日に日本に出願された特願2016-053234号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a hot metal preliminary treatment method.
This application claims priority based on Japanese Patent Application No. 2016-053234 for which it applied to Japan on March 17, 2016, and uses the content here.
本実施形態に係る溶銑予備処理方法では、転炉スラグの低融点化を促す物質として、Al2O3、MnO、FeO、K2O、Li2O、Na2O、CaF2、MgO、SrOの各成分を転炉スラグとともに添加し、転炉スラグの粒径を小さく整粒する。これにより、転炉スラグを速やかに溶融させて滓化率を向上させるとともに、精錬効率の向上、すなわち精錬剤として追加利用する生石灰量の削減と脱P率の向上を図ることができる。 Here, the melting point of the converter slag is about 1400 ° C., and the lump of the converter slag itself does not melt at the hot metal pretreatment temperature of about 1300 ° C. to 1350 ° C.
In the hot metal preliminary treatment method according to the present embodiment, Al 2 O 3 , MnO, FeO, K 2 O, Li 2 O, Na 2 O, CaF 2 , MgO, and SrO are used as substances that promote the low melting point of the converter slag. Are added together with the converter slag, and the particle size of the converter slag is reduced. As a result, the converter slag can be rapidly melted to improve the hatching rate, and the refining efficiency can be improved, that is, the amount of quick lime additionally used as a refining agent can be reduced and the P removal rate can be improved.
そして、このように整粒した後の転炉スラグを上述の精錬剤としてリサイクルするために、溶銑予備処理容器内に投入する(第2の工程)。 In the hot metal preliminary treatment method according to the present embodiment, the converter slag obtained at the time of converter refining (de-C) is discharged, cooled, and then sieved into fine particles to obtain a particle size (equivalent sphere diameter). ), The ratio of the converter slag having a particle size of 20 mm or more and less than 25 mm in the converter slag is 10% by mass or more and less than 15% by mass with respect to the total amount of the converter slag. (First step).
And in order to recycle the converter slag after sizing as mentioned above as the above-mentioned refining agent, it is put into the hot metal pretreatment container (second step).
転炉スラグの粒径を粒径3mm以上とすることで、集塵により投入した転炉スラグの一部又は全部が反応容器の外に散逸することを抑制し、十分に反応に寄与させることができる。そのため、追加で使用する生石灰量を抑制することができる。転炉スラグの粒径を25mm未満とすることで、転炉スラグの比表面積を大きく確保することができ、スラグの溶融時間を短縮できるため、滓化率が上昇する。これによって精錬効率が上昇するため、追加で使用する生石灰量を抑制することができる。 By setting the particle size of the converter slag in the range of 3 mm or more and less than 25 mm, the reaction interface area is increased and heat transfer is promoted, so that the converter slag can be rapidly melted.
By making the particle size of the converter slag 3 mm or more, it is possible to suppress part or all of the converter slag introduced by dust collection from dissipating outside the reaction vessel, and to fully contribute to the reaction. it can. Therefore, the amount of quicklime used additionally can be suppressed. By setting the particle size of the converter slag to less than 25 mm, a large specific surface area of the converter slag can be secured, and the melting time of the slag can be shortened, so that the hatching rate increases. Since refining efficiency rises by this, the amount of quicklime used additionally can be controlled.
従って、転炉スラグの全量に対して、粒径20mm以上(かつ25mm未満)の転炉スラグの比率がグラフ中の矢印で示された範囲にあること、すなわち上述のような転炉スラグの粒径の条件を満たすことにより、操業を阻害することなく、精錬剤として効率良く転炉スラグを再利用することができる。 According to the result of FIG. 2, when the ratio of the converter slag having a particle size of 20 mm or more (and less than 25 mm) is 10% by mass or more with respect to the total amount of the converter slag, the ratio of occurrence of clogging of the input hopper is low, There is no significant hindrance to operations. Moreover, when the ratio of the converter slag having a particle size of 20 mm or more (and less than 25 mm) is less than 15% by mass with respect to the total amount of the converter slag, the conversion rate of the converter slag increases.
Therefore, the ratio of the converter slag having a particle size of 20 mm or more (and less than 25 mm) to the total amount of the converter slag is in the range indicated by the arrow in the graph, that is, the grains of the converter slag as described above. By satisfying the diameter condition, the converter slag can be efficiently reused as a refining agent without hindering operation.
Al2O3の添加量が10.0質量%未満の場合、スラグ粘度の増加が抑制され、スラグの泡立ちが抑制されるため、スラグが反応容器から溢れるスロッピング発生の確率を低くすることができる。 When the addition amount of Al 2 O 3 is 1.0 mass% or more, the effect of lowering the melting point of the slag is sufficiently obtained, and the melting point of the slag becomes 1250 ° C. or less, which is the hot metal temperature, and the hatching rate is improved. As a result, the amount of quicklime used additionally can be suppressed.
When the addition amount of Al 2 O 3 is less than 10.0% by mass, an increase in slag viscosity is suppressed and foaming of slag is suppressed, so that the probability of occurrence of slopping in which slag overflows from the reaction vessel may be lowered. it can.
MnOの添加量については、10.0質量%を超えて添加しても、効果の面で大きな変化は見られない。よって、コストを抑えるため、好ましくはMnOの添加量を10.0質量%以内とする。MnO源としては、例えば、マンガン鉱石を30mm程度に粉砕したものを使用することができる。MnOを投入する第4の工程は、Al2O3を投入する第3の工程と同時、第3の工程の前、あるいは第3の工程の後のいずれであってもよい。 When the amount of MnO added is 0.3% by mass or more, an effect of suppressing an increase in slag viscosity can be obtained. As a result, the probability of occurrence of slopping can be reduced.
About the addition amount of MnO, even if it adds exceeding 10.0 mass%, a big change is not seen by the surface of an effect. Therefore, in order to suppress the cost, the amount of MnO added is preferably within 10.0% by mass. As the MnO source, for example, a manganese ore pulverized to about 30 mm can be used. The fourth step of adding MnO may be performed simultaneously with the third step of adding Al 2 O 3 , before the third step, or after the third step.
尚、Al2O3源として二次精錬スラグを用いない場合は、ボーキサイト、ギブサイトなどのAl2O3含有鉱物や廃アルミナレンガなどを用いることができる。 As described above, the recycling of secondary smelting slag as an Al 2 O 3 source reduces the amount of slag generated in the steelmaking process (from the hot metal pretreatment process to the converter refining process to the secondary refining process). It is equivalent and can reduce the cost and environmental burden associated with slag disposal. That is, since the amount of secondary refining slag used matches the amount of emission reduction outside the slag system, the amount of secondary refining slag used can reduce the cost and environmental load associated with slag disposal.
When secondary refining slag is not used as the Al 2 O 3 source, Al 2 O 3 -containing minerals such as bauxite and gibbsite, waste alumina bricks, and the like can be used.
これにより、精錬効率の向上を実現することができる。酸化鉄源としては、鉄鉱石の他、粉鉱石を焼結して塊状にしたものや、スケール粉やダストを成型したペレットなどを使用することができる。
第5の工程は、第1の工程より後でかつ第2の工程より前、又は、第2の工程と同時であることが好ましい。 The above-mentioned FeO is used as a solid oxygen source during hot metal pretreatment. It is preferable to have a fifth step of charging 1.0% by mass or more and less than 20.0% by mass of iron oxide into the hot metal pretreatment vessel with respect to 100% by mass of the above converter slag.
Thereby, the improvement of refining efficiency is realizable. As the iron oxide source, in addition to iron ore, powdered ore sintered into a lump, pellets formed from scale powder and dust, and the like can be used.
The fifth step is preferably after the first step and before the second step, or at the same time as the second step.
転炉精錬と溶銑予備処理を別々の精錬容器で行う操業形態の他に、転炉精錬と溶銑予備処理を同一の転炉を交互に使用して行う操業形態にも適用することができる。 The method for charging the converter slag and the hatching accelerator such as Al 2 O 3 , MnO, FeO, K 2 O, Li 2 O, Na 2 O, CaF 2 , MgO, SrO, etc. is not particularly limited. It may be added to the hot metal pretreatment container at the time of pretreatment.
In addition to an operation mode in which converter refining and hot metal pretreatment are performed in separate smelting vessels, it can be applied to an operation mode in which converter refining and hot metal pretreatment are alternately performed using the same converter.
本実施形態に係る溶銑予備処理方法は、前記転炉スラグの粒径が3mm以上25mm未満の範囲となり、前記転炉スラグのうち、粒径20mm以上25mm未満の転炉スラグの比率が前記転炉スラグの全量に対して10質量%以上15質量%未満となるように前記転炉スラグを整粒する第1の工程を有する。
また、本実施形態に係る溶銑予備処理方法は、整粒後の前記転炉スラグを溶銑予備処理容器内に投入する第2の工程を有する。
また、本実施形態に係る溶銑予備処理方法は、前記第1の工程より後でかつ前記第2の工程より前、又は、前記第2の工程と同時に、前記転炉スラグ100質量%に対して1.0質量%以上10.0質量%未満のAl2O3を前記溶銑予備処理容器内に投入する第3の工程を有する。
また、本実施形態に係る溶銑予備処理方法は、前記溶銑予備処理容器内に、前記転炉スラグ100質量%に対して0.3質量%以上10.0質量%未満のMnOを投入する第4の工程を有する。
これにより、溶銑予備処理容器内のスラグの粘度を上昇させることなく転炉スラグの滓化を促進することができるため、スラグの系外排出量の削減を図るとともに、スロッピングの発生を回避し、精錬剤として使用する生石灰の使用量を削減することができる。 As described above, the hot metal preliminary treatment method according to the present embodiment recycles the converter slag obtained when the hot metal having undergone the hot metal pretreatment process is refined as a refining agent for hot metal pretreatment. It is.
In the hot metal preliminary treatment method according to the present embodiment, the particle size of the converter slag is in a range of 3 mm or more and less than 25 mm, and the ratio of the converter slag having a particle size of 20 mm or more and less than 25 mm among the converter slag is the converter. It has the 1st process of sizing the said converter slag so that it may become 10 to 15 mass% with respect to the whole quantity of slag.
Moreover, the hot metal pretreatment method according to the present embodiment includes a second step of charging the converter slag after sizing into a hot metal pretreatment container.
Further, the hot metal preliminary treatment method according to the present embodiment is based on 100% by mass of the converter slag after the first step and before the second step, or simultaneously with the second step. There is a third step in which Al 2 O 3 of 1.0% by mass or more and less than 10.0% by mass is charged into the hot metal pretreatment container.
Further, in the hot metal pretreatment method according to the present embodiment, MnO of 0.3% by mass or more and less than 10.0% by mass with respect to 100% by mass of the converter slag is introduced into the hot metal pretreatment container. It has the process of.
As a result, hatching of the converter slag can be promoted without increasing the viscosity of the slag in the hot metal pretreatment vessel, so that the amount of slag discharged outside the system can be reduced and the occurrence of slopping can be avoided. The amount of quicklime used as a refining agent can be reduced.
以下に、本発明に係る溶銑予備処理方法の効果を確認すべく、実施した実験例の結果等について説明する。
先ず、溶銑予備処理工程を経た溶銑を転炉精錬する際に得られる転炉スラグを、冷却した後、細粒化したものを篩い分けて、下記の表1に示す粒径とした転炉スラグの細粒を得た。 [Example]
Below, the result of the experiment example etc. which were implemented in order to confirm the effect of the hot metal preliminary processing method concerning this invention is demonstrated.
First, the converter slag obtained when refining the hot metal that has undergone the hot metal pretreatment process is cooled, and then the finely divided particles are sieved to obtain the converter slag having the particle sizes shown in Table 1 below. Obtained fine granules.
尚、表1の中で、「二次精錬スラグ割合(質量%)」の欄に値の記載がある実験例では、投入されるAl2O3は、二次精錬スラグ中に含まれるAl2O3に由来するものである。 With respect to 100% by mass (total amount) of the granule of the converter slag, Al 2 O 3 and MnO in the proportions shown in Table 1 below and other auxiliary materials were charged into the hot metal pretreatment container. And de-P process was performed on the conditions which made other refining conditions the same.
Incidentally, in Table 1, in the experimental examples are described in the column of the value of the "secondary refining slag ratio (wt%)", Al 2 O 3 to be turned on, Al 2 contained in secondary refining slag It is derived from O 3 .
また、転炉スラグの融点は、本発明を実施しない場合は1400℃程度であった。転炉スラグの融点を溶銑温度である1350℃以下に低下させれば、滓化率が向上して精錬効率の改善が見込める。 Incidentally, the P removal rate must be 80% or more in order to satisfy the P concentration allowed for the product. The amount of additional quicklime in the decarburization furnace is adjusted in order to achieve a de-P ratio of 80% or more. In the case where the present invention is not carried out, the ratio of additional quicklime is 60 to 90%.
Further, the melting point of the converter slag was about 1400 ° C. when the present invention was not carried out. If the melting point of the converter slag is lowered to the hot metal temperature of 1350 ° C. or less, the hatching rate is improved and the refining efficiency can be improved.
転炉スラグの滓化率は、(精錬終了後のスラグ中CaO濃度)/(転炉スラグが全て溶解したときのCaO濃度)×100(%)として定義され、これが40(%)を超える値であれば精錬材としての生石灰使用量を削減することができるため、精錬効率を改善できたと判断した。 When the occurrence rate of clogging of auxiliary material input hopper exceeds 10%, the operation is greatly hindered. Therefore, it is essential that the occurrence rate of clogging of auxiliary material input hopper is less than 10%.
The hatching rate of converter slag is defined as (CaO concentration in slag after refining) / (CaO concentration when all converter slag is dissolved) × 100 (%), which is a value exceeding 40 (%) Then, it was judged that the amount of quicklime used as a refining material could be reduced, so that the refining efficiency could be improved.
Claims (4)
- 溶銑予備処理工程を経た溶銑を転炉精錬する際に得られる転炉スラグを、溶銑予備処理用の精錬剤としてリサイクルする溶銑予備処理方法であって、
前記転炉スラグの粒径が3mm以上25mm未満の範囲となり、前記転炉スラグのうち、粒径20mm以上25mm未満の転炉スラグの比率が前記転炉スラグの全量に対して10質量%以上15質量%未満となるように前記転炉スラグを整粒する第1の工程と;
整粒後の前記転炉スラグを溶銑予備処理容器内に投入する第2の工程と;
前記第1の工程より後でかつ前記第2の工程より前、又は、前記第2の工程と同時に、前記転炉スラグ100質量%に対して1.0質量%以上10.0質量%未満のAl2O3を前記溶銑予備処理容器内に投入する第3の工程と;
前記溶銑予備処理容器内に、前記転炉スラグ100質量%に対して0.3質量%以上10.0質量%未満のMnOを投入する第4の工程と;
を有することを特徴とする溶銑予備処理方法。 A hot metal pretreatment method for recycling converter slag obtained when refining hot metal after the hot metal pretreatment process as a refining agent for hot metal pretreatment,
The converter slag has a particle size of 3 mm or more and less than 25 mm, and the ratio of converter slag having a particle size of 20 mm or more and less than 25 mm in the converter slag is 10% by mass or more and 15% by mass with respect to the total amount of the converter slag. A first step of sizing the converter slag so as to be less than mass%;
A second step of charging the converter slag after sizing into a hot metal pretreatment container;
It is 1.0 mass% or more and less than 10.0 mass% with respect to 100 mass% of the converter slag after the first process and before the second process or simultaneously with the second process. A third step of charging Al 2 O 3 into the hot metal pretreatment container;
A fourth step of charging 0.3% by mass or more and less than 10.0% by mass of MnO to 100% by mass of the converter slag in the hot metal pretreatment container;
A hot metal pretreatment method characterized by comprising: - 前記Al2O3が、転炉精錬工程を経た溶鋼を二次精錬する際に得られる二次精錬スラグに含まれるAl2O3である
ことを特徴とする請求項1に記載の溶銑予備処理方法。 Said Al 2 O 3, molten iron pretreatment according to claim 1, characterized in that the Al 2 O 3 contained molten steel passing through the converter refining step secondary refining slag obtained when the secondary refining Method. - 更に、前記第1の工程より後でかつ前記第2の工程より前、又は、前記第2の工程と同時に、前記転炉スラグ100質量%に対し、FeO換算で1.0質量%以上20.0質量%未満の酸化鉄を前記溶銑予備処理容器内に投入する第5の工程を有する
ことを特徴とする請求項1又は2に記載の溶銑予備処理方法。 Further, after the first step and before the second step, or simultaneously with the second step, 1.0% by mass or more in terms of FeO with respect to 100% by mass of the converter slag. The hot metal pretreatment method according to claim 1, further comprising a fifth step of charging less than 0% by mass of iron oxide into the hot metal pretreatment container. - 更に、前記第3の工程と同時に、前記溶銑予備処理容器内に、前記転炉スラグ100質量%に対し、K2O、Li2O、Na2O、MgO、CaF2、SrOのうち1種又は2種以上をそれぞれ0.3質量%以上5.0質量%未満投入する第6の工程を有する
ことを特徴とする請求項1から3のいずれか1項に記載の溶銑予備処理方法。 Further, at the same time as the third step, one kind of K 2 O, Li 2 O, Na 2 O, MgO, CaF 2 , and SrO with respect to 100% by mass of the converter slag in the hot metal pretreatment container. Alternatively, the hot metal preliminary treatment method according to any one of claims 1 to 3, further comprising a sixth step of adding at least two kinds of them in an amount of 0.3 mass% or more and less than 5.0 mass%.
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