KR20040042542A - Dephosphorization agent of molten iron bag filter dust of electric furnace - Google Patents
Dephosphorization agent of molten iron bag filter dust of electric furnace Download PDFInfo
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- KR20040042542A KR20040042542A KR1020020070853A KR20020070853A KR20040042542A KR 20040042542 A KR20040042542 A KR 20040042542A KR 1020020070853 A KR1020020070853 A KR 1020020070853A KR 20020070853 A KR20020070853 A KR 20020070853A KR 20040042542 A KR20040042542 A KR 20040042542A
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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
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/02—Dephosphorising or desulfurising
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- 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
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Abstract
Description
본 발명은 고로에서 출선된 용선중에 포함된 인(P)을 제거하기 위한 탈인제에 관한 것으로서, 보다 상세하게는 국내 폐기물 처리법에 따라 특정 폐기물로 분류되어 매립되는 전기로 더스트를 산화제로서 이용한 용선탈인제에 관한 것이다.The present invention relates to a dephosphorization agent for removing phosphorus (P) contained in the molten iron from the blast furnace, more specifically molten iron deburring using the electric furnace dust is classified as a specific waste in accordance with the domestic waste disposal method as an oxidant It is about Inje.
일반적으로 용선중의 인(燐,[P])은 불순물로 함유된 원소로써 강의 재질을 저하시키는 대표적인 원소이기 때문에 용선 예비처리(豫備處理) 단계에서 제거하거나 전로 산화정련 단계에서 다음의 (1)식과 같은 반응으로 제거되는 원소이다.In general, phosphorus ([P]) in molten iron is an element contained as an impurity and is a representative element that degrades the steel material. Therefore, phosphorus (P) in molten iron is removed in the molten iron pretreatment step or in the converter oxidation refining step (1). Is an element that is removed by a reaction such as
2P+ 5/2*O2= (P2O5) ------- (1)2P + 5/2 * O 2 = (P 2 O 5 ) ------- (1)
용선중에 함유되어 있는 [P]는 산소분압이 높은조건하에서 기체산소 또는 고체산화제를 이용하여 (1)식과 같은 반응식에 의해서 제거되는 데, 이는 용선중의 [P]가 용선중에 공급되는 산소와 반응하여 (P2O5)라는 산화물을 생성함으로써 제거된다. (1)식과 같이 계속적으로 탈[P] 반응이 일어나기 위해서는 산화생성물인 (P2O5)가 역반응에 의해 재차 환원되지 않아야 한다.[P] contained in molten iron is removed by the reaction formula (1) using gaseous oxygen or solid oxidizer under high oxygen partial pressure. This means that [P] in molten iron reacts with oxygen supplied in molten iron. To form an oxide called (P 2 O 5 ). In order for de [P] reaction to occur continuously as in (1), the oxidation product (P 2 O 5 ) must not be reduced again by reverse reaction.
이와 같이 역반응에 의해 재환원의 방지를 위해서는 불안정한 상태로 용선 슬래그중에 존재하는 (P2O5)를 (1)식 처럼 반응할 수 있도록 용선중에 생석회(CaO)를 첨가하여 (P2O5)를 안정한 상태로 존재 할 수 있는 복합 산화물(3CaO.P2O5,인산염)형태로 고정시키는 것이 필요하며, 이에 대한 반응식은 (2)식과 같다.Thus, present in the molten iron slag in an unstable state in order to prevent the jaehwan won by the reverse reaction (P 2 O 5) the subject to calcium oxide (CaO) added into molten iron to react like the equation (1) (P 2 O 5) It is necessary to fix in the form of a complex oxide (3CaO.P 2 O 5 , phosphate) that can be present in a stable state, the reaction equation is as shown in (2).
3 CaO + (P2O5) = (3 CaO.P2O5) ------- (2)3 CaO + (P 2 O 5 ) = (3 CaO.P 2 O 5 ) ------- (2)
즉, 탈인제는 용선중의 불순물인 [P]를 산화 시킬수있는 산화제와 산화반응에 의해서 생성된 (P2O5)를 보다 안정한 화합물로 만들어주는 조재제(造滓劑)인 생석회(CaO)로 구분되며, 이들의 특성이 탈[P] 효율을 좌우하게 된다.In other words, the dephosphorization agent is an oxidant capable of oxidizing [P], which is an impurity in molten iron, and a quicklime (CaO), which is a preparation agent that makes (P 2 O 5 ) produced by the oxidation reaction into a more stable compound. It is divided into, the characteristics of these will determine the de- [P] efficiency.
일반적으로 용선 탈인제로 사용되고있는 원료로는 산화제로서는 주로 기체산소 또는 고체산화철이 사용되고 있으며, 조재제로서는 (P2O5)와 친화력이 강한 생석회(CaO) 또는 석회석(CaCO3) 및 소오다회(Na2CO3) 등이 사용되고 있다.In general, as a raw material used as a molten iron dephosphorizer, gaseous oxygen or solid iron oxide are mainly used as an oxidizing agent, and as a crude agent, quicklime (CaO) or limestone (CaCO 3 ) and soda ash having strong affinity with (P 2 O 5 ). (Na 2 CO 3 ) and the like are used.
또한, 슬래그의 유동성을 향상시키고 재화를 촉진시키기 위해서 CaF2등의저융점의 원료가 매용제로서 첨가되고 있다.In addition, raw materials of low melting point, such as CaF 2 , are added as solvents in order to improve the fluidity of slag and promote goods.
한편, 폐기물 또는 부산물로서 종전에는 거의 대부분 폐기되어 오던 밀스케일(Mill scale), 소결더스트 및 전로 건식더스트등이 자원의 재활용차원에서 산화제로서 사용되어 오고 있으며, 매용제로서 CaF2, CaCl2가 사용되어 왔으나 다음과 같은 문제점이 있다.Meanwhile, mill scale, sinter dust and converter dry dust, which have been mostly discarded as wastes or by-products, have been used as oxidizing agents in terms of recycling resources. CaF 2 and CaCl 2 are used as solvents. However, there are the following problems.
산화제로서,As an oxidant,
첫째 밀스케일은 제철소의 부산물이기 때문에 회수는 용이하지만 입자가 불균일하여 재차 분쇄가공 공정을 거처야 하기 때문에 가공비가 상승되어 비경제적이며, 또한 분체상태로 취입 할 경우 취입배관의 마모가 발생하는 단점을 가지고 있다.First, mill scale is easy to recover because it is a by-product of steel mills, but the processing costs are increased due to uneven particles and the grinding process must be re-processed, and it is uneconomical when blown into powder. Have.
둘째 소결더스트는 철광석의 소결과정에서 얻어지는 제철소의 부산물이라는 장점과 소결더스트중에 생석회(CaO)가 함유되어 있어 별도로 추가하는 생서회의 첨가량을 줄일수 있다는 장점이 있다. 그러나 환원제로 작용하는 카본(Carbon)과 유황(硫黃)이 함유되어 있어 탈인효율이 저조하며, 탈인처리중 용선중에 유황이 상승하는 복황이 발생되므로 탈인처리후 별도로 탈황처리를 해야되는 문제가 있다.Second, the sintered dust has the advantage of being a by-product of the steel mill obtained in the sintering process of iron ore and the quick-burning ash (CaO) contained in the sintered dust can reduce the amount of added raw fish ash separately. However, since carbon and sulfur which act as reducing agents are contained, dephosphorization efficiency is low, and sulfur is raised during molten iron during the dephosphorization process. .
셋째 전로건식더스트는 전로취련공정에서 발생하는 제철소 부산물이라는 장점은 있으나 원료가 고온상태로 발생하기 때문에 별도로 상온상테에서 냉각을 필요로하고 취급상의 어려운 문제점을 가지고 있다.Thirdly, the converter dry dust has the advantage of being a by-product of steelworks generated in the converter scavenging process, but since the raw material is generated at a high temperature, it requires cooling at room temperature and has a difficult problem in handling.
매용제로서 CaF2는 슬래그의 재화를 촉진시킨다는 잇점은 있으나, 다량첨가시 반응용기의 내화물의 용손을 증대시키는 단점을 가지고 있다.CaF 2 as a solvent has the advantage of facilitating slag goods, but has a disadvantage of increasing the melting loss of the refractory of the reaction vessel when a large amount is added.
본발명은 상기와 같은 문제점을 해결하기 위하여 창안된 것으로서, 탈인제의 산화제로서 전기로 집진기에서 발생하는 백필터더스트와 매용제로서 염화나트륨을 용선의 탈인제로 사용함으로써 생석회 사용량의 일부를 대체할 수 있고, 우수한 탈인효과를 얻음과 동시에 폐자원을 유효하게 활용할 수 있는 전기로 더스트를 이용한 용선 탈인제를 제공하는데 그 목적이 있다.The present invention was devised to solve the above problems, and it is possible to replace part of the quicklime consumption by using sodium chloride as a dephosphorizing agent of molten iron as a bag filter dust generated in an electric dust collector as an oxidizing agent of a dephosphorizing agent and a solvent. The purpose of this invention is to provide a molten iron dephosphorization agent using electric dust which can obtain effective dephosphorization effect and effectively utilize waste resources.
도 1은 본발명 실시예에서 사용한 실험로의 개략도1 is a schematic view of an experiment furnace used in the embodiment of the present invention
<도면의 주요부분에 대한 부호의 설명><Description of the symbols for the main parts of the drawings>
1: 용선 2: 용선탈인제 3: 알루미나도가니1: charter 2: chartering agent 3: alumina crucible
4: 보호도가니 5: 회전식 교반기 6: 유도코일4: Crucible 5: Rotary stirrer 6: Induction coil
상기 목적을 달성하기 위한 본 발명의 용선 탈인제에 있어서, 생석회, 산화제 및 매용제를 혼합하여 제조한 1mm이하의 분체로 이루어지며, 그 조성이 중량%로 생석회가 13~20%, 전기로 백필터더스트가 60~77% 및 염화나트륨이 10~20%의 조성으로 이루어진 것을 특징으로 하는 전기로 백필터더스트를 이용한 용선 탈인제를 특징으로 한다.In the molten iron dephosphorizing agent of the present invention for achieving the above object, made of a powder of less than 1mm prepared by mixing quicklime, an oxidizing agent and a solvent, the composition is 13% to 20% by weight of lime, electric bag filter It is characterized by a molten iron dephosphorization agent using an electric bag filter dust, characterized in that the composition of the dust 60 ~ 77% and sodium chloride 10 ~ 20%.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 국내 폐기물 처리법에 따라 특정 폐기물로 분류되어있는 전기로 의 집진기에서 발생하는 백필터더스트를 유효하게 활용하기 위해 탈인제의 산화제로서 사용했으며 매용제로서 염화나트륨(NaCl)을 사용하였다.The present invention was used as an oxidizing agent of the dephosphorization agent and sodium chloride (NaCl) as a solvent to effectively utilize the bag filter dust generated in the dust collector of the electric furnace classified as a specific waste according to the domestic waste disposal method.
다음의 표 1은 전기로 백필터더스트를 종래의 밀스케일, 소결더스트 및 전로건식더스트와의 화학성분을 비교하기 위해 나타낸 것이다.Table 1 below shows the furnace bag filter dust to compare the chemical composition of the conventional mill scale, sintered dust and converter dry dust.
상기표 1에서 보면 본 발명 탈인제의 산화제로서 전기로 백필터 더스트는 종전의 탈인제의 산화제로 사용되는 밀스케일이나 소결더스트 및 전로건식더스트와 거의 동등의 입도를 가지고 있기 때문에 밀스케일과 같이 별도의 파쇄공정을 거치지 않아도 되는 장점을 가지고 있으며, CaO 를 포함하고 있어 추가로 투입하는 생석회 투입량의 일부를 대체할 수 있어서 경제적이다.In Table 1, the furnace bag filter dust as the oxidizing agent of the dephosphorizing agent of the present invention has a particle size almost equivalent to that of the mill scale, sintered dust, and converter dry dust used as the oxidizing agent of the conventional dephosphorizing agent. It has the advantage of not having to go through the crushing process, and because it contains CaO, it is economical because it can replace a part of the added quicklime input.
즉, 본 발명 탈인제의 산화제로서 전기로 백필터더스트는 60∼77중량%로 투입하는 것이 바람직한데, 77%를 초과하게 되면 CaO함량이 상대적으로 적어지게 되어 탈인효율이 낮아지는 문제가 있으며, 60% 미만이 되면 산화제함량이 적어지게 되어 탈인반응이 미흡하므로 탈인효율이 감소하게 된다. 또한 생석회는 20%를 초과해서 투입하면 전기로 백필터더스트의 함량이 적어져서 상대적으로 산화제 함량이 낮아지므로 탈인효과가 떨어지며, 또한 13%보다 함량이 적을 경우 염기도가 적어져서 P2O5를 보다 안정한 화합물로 만들어줄 수 없어서 탈인효율이 떨어진다.That is, the oxidizing agent of the present invention, it is preferable to add the electric bag filter dust at 60 to 77% by weight, but if the content exceeds 77%, the CaO content is relatively low, so the dephosphorization efficiency is lowered. If the amount is less than 60%, the oxidant content decreases and the dephosphorization reaction is insufficient, thereby reducing the dephosphorization efficiency. In addition, if lime is added in excess of 20%, the content of bag filter dust is lowered by electricity, so the oxidizing agent content is lowered, so the dephosphorization effect is lowered. If the content is less than 13%, the basicity is less and P 2 O 5 is lowered. Dephosphorization efficiency is low because it cannot be made into a stable compound.
또한, 전기로 백필터더스트는 소결더스트, 전로 건식더스트에 비하여 탈인조업에 영향을 미치는 C 와 S가 거의 포함되지 않아 탈인효율이 우수한 장점을 가지고 있다.In addition, the electric furnace bag filter dust has an advantage in that the dephosphorization efficiency is excellent because almost no C and S are included in the dephosphorization operation compared with the sinter dust and the converter dry dust.
상기 표1의 전기로 백필터더스트의 화학성분 조건은 집진되는 시기에 따라약간씩 차이가 있으며 각 조성별로 ±10% 내외로서 CaO : 8 ~ 18 중량% , T.Fe : 47~ 53%, SiO2: 0.5 ~ 3 중량% 및 기타 소량의 불순물로 조성된다.The chemical composition of the electric furnace bag filter dust of Table 1 is slightly different depending on the time of dust collection, and each composition is about ± 10%, CaO: 8-18% by weight, T.Fe: 47-53%, SiO 2 : 0.5 to 3% by weight and other small amounts of impurities.
또한, 본 발명 탈인제의 매용제로서 염화나트륨(융점 804℃, 비점 1413℃, 비중 2.163))은 식 (3)처럼 고온의 용선온도에서 용선중의 [P]와 직접반응하여 인화나트륨(Na3P)을 형성하여 효과적으로 용선중의 [P]를 제거하고, 발생되는 염소가스는 화학반응시 용선내 혼합성능을 증대하여 탈인반응을 촉진시켜준다.In addition, sodium chloride (melting point 804 DEG C, boiling point 1413 DEG C, specific gravity 2.163) as a solvent of the dephosphorizing agent of the present invention was directly reacted with sodium phosphate (Na 3 P) by reacting directly with [P] in molten iron at a high molten iron temperature as shown in Eq. ) To effectively remove [P] in molten iron, and the chlorine gas generated promotes dephosphorization by increasing the mixing performance in molten iron during chemical reaction.
6 NaCl (l) + 2 [P] → 2 Na3P (g) + 3 Cl2(g) ------- (3)6 NaCl (l) + 2 [P] → 2 Na 3 P (g) + 3 Cl 2 (g) ------- (3)
그러나 염화나트륨은 과잉으로 혼합하면 고온에서 지나친 가스발생으로 인한 작업환경이 열악해지므로 적정량의 혼합이 필요하다.However, when sodium chloride is mixed excessively, the working environment is poor due to excessive gas generation at high temperature, so an appropriate amount of mixing is required.
이하 본 발명에 대하여 실시예에 의거 상세히 설명한다.Hereinafter, the present invention will be described in detail with reference to Examples.
본 발명에 따른 산화제와 매용제를 이용한 용선탈인제의 조성(wt%)은 표 2와 같으며 본 발명의 용선 탈인제와 비교하기 위하여 밀스케일, 소결더스트, 전로 건식더스트를 이용한 탈인제를 비교제로 표시 하였다.The composition (wt%) of the molten iron dephosphorization agent using the oxidizing agent and the solvent according to the present invention is shown in Table 2, and in order to compare with the molten iron dephosphorization agent of the present invention, the dephosphorization agent using mill scale, sinter dust, converter dry dust as a comparative agent is used. Marked.
용선탈인시험은 도 1에 도시한 바와 같이 알루미나도가니(3) 외측에 보호도가니(4)를 구비하고 그 보호도가니 외측 유도코일(6)이 내장된 고주파유도용해로(실험로)를 이용하여 알루미나도가니에 인농도가 0.1중량%인 용선30 Kg을 용해시킨후 표 2와 같은 4종류의 입도가 1mm이하인 용선탈인제(2)를 용선중앙부에 회전식 교반기(5)를 침적하여 회전속도 120 rpm으로 교반하였다.The molten iron dephosphorization test is performed by using a high-frequency induction melting furnace (experimental furnace) having a protective crucible (4) outside the alumina crucible (3) and a protective crucible outer induction coil (6) as shown in FIG. After dissolving 30 kg of molten iron having a phosphorus concentration of 0.1% by weight in a crucible, four types of molten iron degreasing agent (2) having a particle size of 1 mm or less were deposited at the center of the molten iron at a rotational speed of 120 rpm. Stirred.
탈인제 투입량은 1500g 으로 동일하게 하였으며, 유지온도는 1350℃ 로 하고 유지시간은 30분으로 일정하게 하였다. 상기 조건으로 탈인제를 용선중에 투입하여 처리한 결과 표 3과 같다.The input amount of dephosphor was the same as 1500g, the holding temperature was 1350 ℃ and the holding time was constant to 30 minutes. The dephosphorization agent was added to the molten iron under the above conditions and treated as shown in Table 3.
표 3에서 보듯이 본 발명제는 매용제로서 형석등을 사용한 비교제1(A), 2(B) 보다 탈인효과가 더욱 우수하며, 비교제3(C)와는 동등한 탈인효과를 나타내었다.As shown in Table 3, the present invention had a better dephosphorization effect than Comparative Agents 1 (A) and 2 (B) using fluorspar, etc., as a solvent, and showed a dephosphorization effect equivalent to Comparative Agent 3 (C).
발명제2(E)와 같이 매용제인 염화나트륨량이 증가시 탈인효과가 향상되는 것을 알수 있으나 매용제량이 20% 이상 초과시 과도한 가스발생으로 인한 작업환경이 열악해지며, 10% 미만시는 슬래그의 유동성 및 재화능이 나빠져서 기대하는 탈인효과를 얻을 수 없다.As described in Inventive 2 (E), the dephosphorization effect is improved when the amount of solvent, sodium chloride, is increased, but when the amount of solvent is more than 20%, the working environment is inferior due to excessive gas generation. Deterioration of the ability to get the expected dephosphorization effect.
또한, 표 4에는 상기 비교제와 본 발명제의 탈인후의 [S] 농도 변화를 나타낸 것으로서 비교제2(B),3(C)는 반응종료시 [S] 농도가 상승되는 것을 알 수 있고, 발명제의 경우는 초기[S] 농도대비 감소하는 효과가 나타남을 알 수 있다.In addition, Table 4 shows the change in concentration of [S] after dephosphorization of the comparative agent and the present invention, and Comparative 2 (B) and 3 (C) shows that the concentration of [S] increases at the end of the reaction. In the case of the invention it can be seen that the effect of reducing the initial [S] concentration.
본 발명에의 의하면, 용선 탈인제의 주원료로 사용되는 전기로 백필터더스트는 지정폐기물로 분류되어 특정한 지역에만 매립되어 왔으나 이를 재활용하여 용선탈인제로 사용함으로써 막대한 매립비용의 절감을 통한 경제적 효과와 또한 더스트 매립시 중금속류의 용출로 인한 토양의 환경오염을 차단할 수 있을 뿐만 아니라 기존의 산화철계 용선 탈인제 보다 우수한 탈인효과와 [S] 농도 저감 효과를 얻을 수 있었다.According to the present invention, the electric furnace bag filter dust used as a main raw material of the molten iron dephosphorization agent has been classified as a designated waste, and has been buried only in a specific area, but it can be recycled and used as a molten iron degreaser to reduce the enormous landfill cost. In addition, it was possible to block the environmental pollution of the soil due to the leaching of heavy metals during dust reclamation, and to obtain a better dephosphorization effect and [S] concentration reduction effect than the conventional iron oxide molten iron dephosphorizer.
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| CN104046748A (en) * | 2014-06-19 | 2014-09-17 | 攀钢集团攀枝花钢铁研究院有限公司 | Molten steel dephosphorizing agent and molten steel dephosphorizing method |
| CN106893801A (en) * | 2015-12-18 | 2017-06-27 | 中国科学院金属研究所 | A kind of electric arc furnaces molten steel extra furnace dephosphorization method |
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| KR930006640B1 (en) * | 1991-10-01 | 1993-07-22 | 포항종합제철 주식회사 | Dephosporus agent for preheat treatmenting of molten metal |
| KR950012403B1 (en) * | 1993-12-22 | 1995-10-17 | 포항종합제철주식회사 | Dephosphorizer |
| KR100270120B1 (en) * | 1996-12-14 | 2000-10-16 | 이구택 | Dephosphorous agent for molten iron |
| KR19990055889A (en) * | 1997-12-29 | 1999-07-15 | 이구택 | Chartering dephosphorizer using converter sludge |
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| CN106893801A (en) * | 2015-12-18 | 2017-06-27 | 中国科学院金属研究所 | A kind of electric arc furnaces molten steel extra furnace dephosphorization method |
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