KR100398413B1 - A method for preventing an ld slag from generating white water - Google Patents
A method for preventing an ld slag from generating white water Download PDFInfo
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- KR100398413B1 KR100398413B1 KR10-1998-0057609A KR19980057609A KR100398413B1 KR 100398413 B1 KR100398413 B1 KR 100398413B1 KR 19980057609 A KR19980057609 A KR 19980057609A KR 100398413 B1 KR100398413 B1 KR 100398413B1
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- slag
- converter slag
- converter
- molten
- furnace
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- 239000002893 slag Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000013535 sea water Substances 0.000 abstract description 16
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000010405 reoxidation reaction Methods 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 239000002244 precipitate Substances 0.000 description 15
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 10
- 239000000292 calcium oxide Substances 0.000 description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 7
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/36—Processes yielding slags of special composition
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
- C04B5/06—Ingredients, other than water, added to the molten slag or to the granulating medium or before remelting; Treatment with gases or gas generating compounds, e.g. to obtain porous slag
-
- 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
- C21C7/0087—Treatment of slags covering the steel bath, e.g. for separating slag from the molten metal
Abstract
본 발명은 전로슬래그의 백탁수 생성 방지 방법에 관한 것으로,The present invention relates to a method of preventing white cloud water generation of converter slag,
해안 매립, 호안 구축용 뒷채움재 또는 매립 재료로 사용되는 전로 슬래그를 사전처리하는데 있어서,In the pretreatment of converter slags used as shorefills, shorefill backfills or landfill materials,
1350℃ 이상의 온도에서 용해로에서 전로 슬래그를 재용융시킨 다음, 용해로로부터 유출되는 용융 슬래그에 공기를 분사하여 전로 슬래그내의 FeO 함량이 0.5%가 될 때까지 상기 용융 전로 슬래그를 재산화시키는 것을 포함하여 이루어지는 백탁수 생성 방지 방법이 제공되며,White turbidity comprising remelting the converter slag in the furnace at a temperature of 1350 ° C. or higher, and then injecting air into the molten slag flowing out of the furnace to reoxidize the molten converter slag until the FeO content in the converter slag is 0.5%. Can prevent generation is provided,
본 발명의 재산화 방법에 의해 사전처리된 전로 슬래그를 바다의 호안용 뒷채움재 또는 매립용으로 사용함으로써 바닷물의 pH에 영향을 주지 않으며 백탁수 생성도 방지할 수 있다.By using the converter slag pretreated by the reoxidation method of the present invention as a backfill material or landfill for sea revetment, it does not affect the pH of seawater and prevents the formation of turbid water.
Description
본 발명은 전로슬래그의 백탁수 생성 방지 방법에 관한 것으로, 보다 상세하게는 재산화 방법을 사용하여 전로 슬래그의 백탁수 생성을 방지하는 방법에 관한 것이다.The present invention relates to a method for preventing the formation of turbid water of converter slag, and more particularly, to a method for preventing the formation of turbid water of converter slag using the reoxidation method.
제철소에서는 제강 공정중에 전로 슬래그가 다량 발생되는데 이는 용선에 산소를 취련하여 용강을 만들 때 용선중에 포함된 불순물을 제거하기 위하여 투입된 생석회가 용선중의 불순물인 Si, P, S 등과 산화반응 하면서 생기는 용재이다. 이러한 전로 슬래그는 현재 일부는 자원 재활용 측면에서 다른 곳에 재활용되고 있으나, 많은 양이 매립되고 있는 실정이다. 따라서 환경 오염원으로 대두되어 이를 해결하기 위해 또 다른 재활용 분야를 찾기 위해 많은 연구가 이루어지고 있다.In steel mills, a large amount of converter slag is generated during the steelmaking process, which is produced by oxidizing the quicklime, which is added to remove molten impurities from molten iron by removing oxygen from molten iron, to Si, P, and S, which are impurities in the molten iron. to be. Some of these converter slags are currently being recycled elsewhere in terms of resource recycling, but a lot of landfills are being buried. Therefore, a lot of research is being conducted to find another recycling field to solve this problem as a source of environmental pollution.
한편, 해안을 매립할 경우 먼저 방파제를 만들고 방파제 안쪽에는 뒷채움재를 넣어서 채움을 실시하고 있다. 이때, 뒷채움재로써 천연쇄석, 고로슬래그, 전로슬래그 등의 골재가 사용된다. 특히 전로슬래그를 사용할 경우에는 바닷물과 접촉하면 전로슬래그 내에 함유되어 있는 칼슘성분이 용출되게 되고 이것이 바닷물 중에 용해되어 있는 탄산이온 등의 성분과 반응하여 석회석(CaCO3)등의 백색침전이 생성된다. 또 이 전로슬래그를 매립한 경우에도 호안을 만들고 이 호안 뒤에는 천연골재, 고로슬래그, 전로슬래그 등의 골재를 채우고 있다. 이 경우에도 호안 뒷채움재로 전로슬래그를 사용하면 바닷물과 반응하여 백색침전이 생성되게 된다.On the other hand, when the coast is reclaimed, the breakwater is first made, and the backfill is put inside the breakwater to fill it. At this time, aggregates such as natural crushed stone, blast furnace slag, converter slag are used as backfill material. In particular, when the converter slag is used, the calcium component contained in the converter slag is eluted when it comes into contact with seawater, and this reacts with components such as carbonate ions dissolved in the seawater to generate white precipitates such as limestone (CaCO 3 ). In addition, even when the converter slag is reclaimed, a revetment is made, and the refill is filled with aggregate such as natural aggregate, blast furnace slag, and converter slag. Even in this case, when the converter slag is used as a backfill material, white precipitates are generated by reacting with seawater.
이에 본 발명의 목적은 전로슬래그를 재산화시킴으로써 전로 슬래그에 의한 백탁수 생성을 방지하는 방법을 제공하는데 있다.It is therefore an object of the present invention to provide a method of preventing white cloud water generation by converter slag by reoxidizing converter slag.
본 발명에 의하면,According to the invention,
해안 매립, 호안 구축용 뒷채움재 또는 매립 재료로 사용되는 전로 슬래그를 사전처리하는데 있어서,In the pretreatment of converter slags used as shorefills, shorefill backfills or landfill materials,
1350℃ 이상의 온도에서 용해로에서 전로 슬래그를 재용융시킨 다음, 용해로로부터 유출되는 용융 슬래그에 공기를 분사하여 전로 슬래그내의 FeO 함량이 0.5%가 될때까지 상기 용융 전로 슬래그를 재산화시키는 것을 포함하여 이루어지는 백탁수 생성 방지 방법이 제공된다.White turbid water comprising remelting the converter slag in the furnace at a temperature of 1350 ° C. or higher, and then injecting air into the molten slag flowing out of the furnace to reoxidize the molten converter slag until the FeO content in the converter slag is 0.5%. A production prevention method is provided.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
산업 폐기물인 전로 슬래그는 통상 표 1과 같은 조성을 갖는 것들이 많다.Converter slag, which is an industrial waste, usually has a composition as shown in Table 1.
표 1에 나타난 바와 같이, 전로 슬래그중에는 CaO, FeO, SiO2등이 가장 많이 함유되어 있다. 이 중 CaO가 바닷물 속의 CO2와 반응하게 되면 CaCO3의 백색 침전을 생성하게 되는데, 이것이 백탁수이다.As shown in Table 1, the converter slag contains most of CaO, FeO, SiO 2 and the like. Of these, when CaO reacts with CO 2 in seawater, it produces a white precipitate of CaCO 3 , which is turbid water.
본 발명에서는 상기 산화 칼슘(CaO)을 안정화시킴으로써 CO2와 반응하는 것을 방지하여 탄산칼슘의 백색침전이 생기지 않도록 하는 것이다.In the present invention, by stabilizing the calcium oxide (CaO) to prevent the reaction with CO 2 to prevent the white precipitate of calcium carbonate.
먼저 산업 현장에서 채취된 전로 슬래그를 용해로에서 1350℃ 이상의 온도로 재용융시킨다. 이는 전로 슬래그의 융점이 약 1330℃이므로 슬래그를 충분히 용융시키기 위해 1350℃ 이상의 온도에서 용융시키는 것이다.First, converter slag collected at industrial sites is remelted in a melting furnace at a temperature of 1350 ° C. or higher. This is because the melting point of the converter slag is about 1330 ° C., so that the slag is melted at a temperature of 1350 ° C. or more to sufficiently melt the slag.
그후 용해로에서 배출되는 용융 전로 슬래그에 공기를 분사하면 하기식 1과 같은 반응이 일어나서 산화 칼슘이 안정하게 된다.Thereafter, when air is injected into the molten converter slag discharged from the melting furnace, a reaction such as the following Equation 1 occurs and calcium oxide is stabilized.
Fe2O3+ 2CaO → 2CaO ·Fe2O3 Fe 2 O 3 + 2CaO → 2CaOFe 2 O 3
상기식 1에서와 같이, 전로 슬래그에 공기를 분사하면 전로 슬래그중에 다량 함유되어 있는 Fe와 FeO가 Fe2O3로 산화된다. 생성된 Fe2O3는 전로 슬래그내에 가장많이 함유되어 있으며 바닷물과 접촉시 백탁수를 침전하는 CaO와 반응하여 안정한 2CaO ·Fe2O3를 생성한다. 이는 Fe2O3는 약산성이며, 반면 CaO는 약알칼리성을 띠므로 서로 결합하여 중성 물질인 2CaO·Fe2O3로 안정화되는 것이다.As in Equation 1, when air is injected into the converter slag, Fe and FeO contained in a large amount in the converter slag are oxidized to Fe 2 O 3 . The produced Fe 2 O 3 is most contained in the converter slag and reacts with CaO, which precipitates turbid water upon contact with sea water, producing stable 2CaO · Fe 2 O 3 . Fe 2 O 3 is weakly acidic, while CaO is weakly alkaline, binding to each other to stabilize 2CaO · Fe 2 O 3 as a neutral material.
이와같이 전로 슬래그내의 CaO를 안정화함으로써 전로 슬래그가 바닷물에 접촉하여도 백색 침전이 일어나지 않도록 하는 것이다.By stabilizing CaO in the converter slag in this way, the white slag does not occur even when the converter slag contacts the seawater.
이 때, 공기 분사는 전로 슬래그내의 FeO의 농도가 0.5% 이하가 될 때까지 행하는데, 이는 FeO가 Fe2O3로 산화되어 농도가 0.5% 이하로 되면 탄산칼슘 침전이 발생하지 않기 때문이다. 한편, 이때 전로 슬래그내의 FeO의 농도는 습식 분석법에 의해 측정하여 FeO의 농도가 0.5%로 될 때까지 공기 분사를 계속하도록 한다.At this time, the air injection is performed until the concentration of FeO in the converter slag becomes 0.5% or less, because the precipitation of calcium carbonate does not occur when FeO is oxidized to Fe 2 O 3 and the concentration becomes 0.5% or less. On the other hand, the concentration of FeO in the converter slag is measured by a wet analysis method to continue the air injection until the concentration of FeO is 0.5%.
상기와 같이, 전로 슬래그를 재산화 방법으로 처리함으로써 전로 슬래그가 바닷물과 접촉시 백탁수의 생성이 방지되며, 바닷물의 pH에도 거의 영향을 미치지 않게된다.As described above, by treating the converter slag by the reoxidation method, the formation of turbid water is prevented when the converter slag is in contact with the seawater, and hardly affects the pH of the seawater.
이하 실시예를 참조로 하여 본 발명에 대해 설명한다.The present invention will be described with reference to the following Examples.
비교예 1Comparative Example 1
제철소에서 채취하였으며 입도가 각각 8mm 이하, 8∼15mm 및 15mm 이상인 전로 슬래그를 비이커에 넣고 바닷물에 침지해 두었다. 이때, 약 30분 후부터 백색의 침전이 생성되기 시작하였다. 시간 경과에 따른 바닷물의 pH 변화와 백색침전 형성을 관찰하여 표 2에 요약하였다.They were taken from steel mills, and the converter slags with particle sizes of 8 mm or less, 8-15 mm and 15 mm or more were placed in beakers and immersed in seawater. At this point, a white precipitate began to form after about 30 minutes. The pH change and the white precipitate formation over time were summarized in Table 2.
표 2에 나타난 바와 같이, 전로 슬래그는 바닷물의 pH 범위인 8.0∼8.2보다 알칼리성이 강하며, 입도가 미세할수록 백색 침전을 많이 발생하고 알칼리성이 강한 용액을 용출한다는 것을 알 수 있다.As shown in Table 2, the converter slag is more alkaline than the pH range of 8.0 to 8.2, and it can be seen that the finer the particle size, the more white precipitates are generated and the more alkaline solution is eluted.
실시예 1Example 1
비교예 1에서 사용한 것과 동일한 전로 슬래그를 사용하여 전로 슬래그를 다음과 같이 전처리하였다.The converter slag was pretreated as follows using the same converter slag as used in Comparative Example 1.
상기 전로 슬래그를 용해로에 넣고 LPG로서 1350℃ 이상으로 재용융하고 용융된 슬래그를 용해로에서 장방형 노즐 사이로 유출시키면서 1mm slit 노즐을 통해 0.3-1.5 기압의 공기를 유출되는 용출슬래그에 분사하여 습식 방법으로 용융슬래그내의 FeO의 함량이 0.5%가 될 때까지 재산화시켰다.The converter slag was put into the melting furnace and remelted at 1350 ° C. or higher as LPG, and the molten slag was injected into the elution slag which flows 0.3-1.5 atm of air through the 1 mm slit nozzle into the elution slag through a 1 mm slit nozzle. It was reoxidized until the content of FeO in the slag became 0.5%.
이와같이 재산화처리된 전로 슬래그를 비이커에 넣고 바닷물을 투입하여 시간 경과에 따른 pH변화 및 백색침전 발생을 관찰하여 표 3에 그 결과를 나타내었다.In this way, put the reclaimed converter slag in the beaker and the seawater was added to observe the pH change and the white precipitate occurrence over time and the results are shown in Table 3.
표 3에 나타난 바와같이, 재산화 처리된 전로 슬래그는 용출물의 pH가 바닷물의 pH 범위보다 약간 알칼리성이 센 것으로 보아, 바닷물의 pH에 거의 영향을 미치지 않으며, 백색 침전도 전혀 발생되지 않았음을 알 수 있다.As shown in Table 3, the reoxidized converter slag showed that the eluate had a slightly higher alkalinity than the pH range of seawater, indicating little effect on the pH of the seawater and no white precipitation. Can be.
실시예 2∼비교예 2Example 2-Comparative Example 2
실시예 1에 기술된 방법을 사용하여 용융 슬래그에 공기분사 시간을 조절하여 전로 슬래그내의 FeO 함량을 조절하였다. 각각 용융 슬래그 중량을 기준으로 FeO 0.5%, 1.3%, 2.9% 및 4.8%를 함유한 슬래그를 바닷물에 침지한 후 15분 동안 관찰하여 그 결과를 표 4에 나타내었다.The air spraying time on the molten slag was controlled using the method described in Example 1 to control the FeO content in the converter slag. Slag containing 0.5%, 1.3%, 2.9% and 4.8% FeO based on the weight of molten slag, respectively, was observed for 15 minutes after immersion in seawater, and the results are shown in Table 4.
표 4에 나타낸 바와 같이, 용융 전로 슬래그내의 FeO 함량이 0.5%가 되도록 공기 분사하여 산화하면 백색 침전이 생성되지 않음을 알 수 있다.As shown in Table 4, it can be seen that the white precipitate is not produced when the air is oxidized by air injection so that the FeO content in the melting converter slag is 0.5%.
상기한 바와 같이, 본 발명의 재산화 방법에 의해 사전처리된 전로 슬래그를 바다의 호안용 뒷채움재 또는 매립용으로 사용함으로써 바닷물의 pH에 영향을 주지 않으며 전로슬래그에 의한 백탁수 생성도 방지할 수 있다.As described above, by using the converter slag pretreated by the reoxidation method of the present invention as a seawater backfill material or landfill, it does not affect the pH of seawater and also prevents the formation of turbid water by the converter slag. have.
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| KR100476811B1 (en) * | 2000-12-21 | 2005-03-17 | 주식회사 포스코 | A pretreatment method of steel slag by using carbon dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5675507A (en) * | 1979-11-21 | 1981-06-22 | Sumitomo Metal Ind Ltd | Regenerating method of converter slag |
| JPS5920415A (en) * | 1982-07-22 | 1984-02-02 | Nippon Kokan Kk <Nkk> | Method for mixing and modifying converter slag |
| WO1998012359A1 (en) * | 1996-09-17 | 1998-03-26 | 'holderbank' Financiere Glarus Ag | Process for reclaiming incineration waste |
| WO2001002359A1 (en) * | 1999-07-01 | 2001-01-11 | Ajinomoto Co., Inc. | Heterocyclic compounds and medicinal use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5675507A (en) * | 1979-11-21 | 1981-06-22 | Sumitomo Metal Ind Ltd | Regenerating method of converter slag |
| JPS5920415A (en) * | 1982-07-22 | 1984-02-02 | Nippon Kokan Kk <Nkk> | Method for mixing and modifying converter slag |
| WO1998012359A1 (en) * | 1996-09-17 | 1998-03-26 | 'holderbank' Financiere Glarus Ag | Process for reclaiming incineration waste |
| WO2001002359A1 (en) * | 1999-07-01 | 2001-01-11 | Ajinomoto Co., Inc. | Heterocyclic compounds and medicinal use thereof |
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