KR20180060095A - METHOD FOR RECOVERING Fe FROM CONVERTER SLAG CONTAINING Fe - Google Patents

METHOD FOR RECOVERING Fe FROM CONVERTER SLAG CONTAINING Fe Download PDF

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KR20180060095A
KR20180060095A KR1020160159190A KR20160159190A KR20180060095A KR 20180060095 A KR20180060095 A KR 20180060095A KR 1020160159190 A KR1020160159190 A KR 1020160159190A KR 20160159190 A KR20160159190 A KR 20160159190A KR 20180060095 A KR20180060095 A KR 20180060095A
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slag
reducing agent
recovering
charge
feo
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Korean (ko)
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정용석
박주현
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한국산업기술대학교산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0006—Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0066—Preliminary conditioning of the solid carbonaceous reductant
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/008—Use of special additives or fluxing agents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/2406—Binding; Briquetting ; Granulating pelletizing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/248—Binding; Briquetting ; Granulating of metal scrap or alloys

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  • Metallurgy (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Mechanical Engineering (AREA)
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Abstract

The present invention relates to an effectively recovering method of FE from steelmaking slag. To the above object, the present invention comprises: a step of providing a reducing agent in hot molten slag; and a step of reducing FeO in the slag by reducing the Fe through reaction of the reducing agent and the slag.

Description

Fe 함유 슬래그 중 Fe의 회수 방법{METHOD FOR RECOVERING Fe FROM CONVERTER SLAG CONTAINING Fe}METHOD FOR RECOVERING FER FROM CONVERTER SLAG CONTAINING Fe

본 발명은 제강 슬래그 내의 유가원소 회수에 관한 것이며, 보다 구체적으로는 제강 슬래그 내의 Fe를 환원제를 이용하여 효율적으로 회수하는 방법에 관한 것이다. More particularly, the present invention relates to a method for efficiently recovering Fe in steelmaking slag using a reducing agent.

제철 제강 공정에서는 필연적으로 슬래그가 발생된다. 슬래그는 부산물이지만 유용 성분이 다량 포함되어 있어, 이를 활용하기 위한 연구가 계속되고 있다. Slag is inevitably generated in the steelmaking process. Although slag is a by-product, it contains a large amount of useful ingredients, and research is underway to utilize it.

그러나 제철 공정에서 유래하는 고로 슬래그가 시멘트 원료로 활발히 재활용 되고 있는 반면, 제강 슬래그는 성분 중 높은 산화철(FeO) 함량으로 인하여 시멘트 혹은 건축 골재로의 재활용이 어려움이 있고, 발생량의 50% 가량이 단순히 성토용 골재로 매립되고 있는 실정이다. However, blast furnace slag derived from iron making process is actively recycled as raw material for cement, whereas steel making slag is difficult to recycle to cement or building aggregate due to its high iron oxide (FeO) content, and about 50% It is currently being landfilled with aggregate aggregates.

제강 슬래그에서 유가금속(Fe또는 Fe-P)이 회수되면 산화철 함량이 낮은 슬래그 조성을 얻게 되므로, 기존 성토용 골재가 아니라 시멘트의 원료로서 사용할 수 있어 슬래그 재활용의 부가가치를 높일 수 있다. If iron (Fe or Fe-P) is recovered from steelmaking slag, slag composition with low iron oxide content can be obtained. Therefore, it can be used as raw material for cement instead of existing aggregate aggregate, thereby increasing added value of slag recycling.

또 제강슬래그부터 Fe-P 합금을 생산하면 주조 공정과 연계하여 고급주물용 소재로 사용할 수 있다. In addition, when Fe-P alloy is produced from steel slag, it can be used as a material for high-grade castings in connection with the casting process.

이러한 문제를 해결하기 위해 종래에는 풍쇄공법을 이용한 슬래그 현열 재활용 및 RHF 공정을 통한 슬래그/분진 내 유가금속 회수 등의 기술적 시도가 있었으나 경제성 및 효율성의 문제로 상용화되기 어려운 실정이다. In order to solve such problems, there have been technical attempts such as slag sensible heat recycling using a crushed stone method and recovery of valuable metals in slag / dust through RHF process, but it is difficult to commercialize them because of economical efficiency and efficiency.

본 발명은 전술한 문제점을 해결하기 위한 것으로서, 제강 슬래그로부터 Fe를 회수하는 방법을 제공하는 것이 목적이다.SUMMARY OF THE INVENTION The present invention is directed to solving the above-mentioned problems, and an object thereof is to provide a method of recovering Fe from steelmaking slag.

상기 목적을 달성하기 위하여, 본 발명에서는 아래와 같은 단계로 이루어지는, Fe 함유 슬래그 중 Fe의 회수 방법을 제공한다. In order to achieve the above object, the present invention provides a method for recovering Fe in Fe-containing slag, comprising the following steps.

고온의 용융 상태 슬래그 내에 환원제를 공급하는 단계; Supplying a reducing agent into the hot molten slag;

상기 환원제와 슬래그의 반응을 통해 슬래그 내의 FeO를 Fe로 환원시켜 회수하는 단계. And reducing the FeO in the slag to Fe through the reaction of the reducing agent and the slag.

제강슬래그는 고온의 열에너지(450MJ/ton-steel)를 내재하고 있으나, 냉각과정을 거쳐 열에너지는 소모되어 버린다. 본 발명에서는 용융 상태에서 환원 공정을 실시하여 산화철 성분을 환원시킨다. 즉 슬래그가 포함하고 있는 현열을 활용하므로 추가 에너지 투입을 최소화할 수 있다. Steelmaking slag contains high-temperature thermal energy (450MJ / ton-steel), but the heat energy is consumed after cooling process. In the present invention, a reduction process is performed in a molten state to reduce the iron oxide component. That is, utilizing the sensible heat contained in the slag, the additional energy input can be minimized.

이때 환원제로서는 Al, C가 바람직하다. At this time, Al and C are preferable as the reducing agent.

환원제로서 Al(Al dross 활용)을 투입할 경우, 아래와 같은 반응에 따라 추가 열량을 확보할 수 있다.When Al (Al dross) is added as a reducing agent, an additional amount of heat can be ensured by the following reaction.

3FeO(L) + 3Al(L) = 3Fe(L) + Al2O3(L) △H = -317.8 KJ/mol of Fe3FeO (L) + 3Al (L) = 3Fe (L) + Al2O3 (L)? H = -317.8 KJ / mol of Fe

이때 반응 후 생성된 Al2O3 및 Al2O3 함유 슬래그에 의해 슬래그 저융점화가 이루어진다. 또 Al을 환원제로 사용하면 액상 영역의 변화로 Fe 회수 조건이 유리하게 된다. At this time, the slag containing Al 2 O 3 and Al 2 O 3 containing slag produced after the reaction has a low melting point. Also, when Al is used as a reducing agent, the conditions for recovery of Fe are advantageous due to the change of the liquid phase region.

환원제로서 탄소를 이용할 경우에는 펠렛 형태로 제조하여 투입하는 것이 바람직하다. 탄소를 펠렛 형태로 형성하면 반응성을 향상시키고, 반응 물질들이 비산되는 것을 방지할 수 있다.When carbon is used as the reducing agent, pellets are preferably prepared and introduced. When the carbon is formed into a pellet shape, the reactivity can be improved and the reactants can be prevented from scattering.

한편, 본 발명에서는 플럭스를 추가로 투입할 수 있다. 플럭스로는 CaF2,CaO, Al 드로스, 레드 머드(FeO, Al2O3가 주성분인 부산물)로 이루어지는 그룹에서 선택되는 어느 하나 이상인 것이 바람직하다. On the other hand, in the present invention, a flux can be further added. The flux is preferably at least one selected from the group consisting of CaF 2, CaO, Al dross, red mud (FeO, a by-product mainly composed of Al 2 O 3).

플럭스를 투입하면 열역학적 혼합 효과에 따라 융점이 낮아지고, 액상 유지 온도 범위를 넓히며, 반응 참여율이 높아지는 효과가 있다. When the flux is added, the melting point is lowered according to the thermodynamic mixing effect, the liquid holding temperature range is widened, and the reaction participation rate is increased.

플럭스도 펠렛 형태로 하는 것이 반응성 향상에 있어서 바람직하다. It is preferable that the flux is also in the form of pellets in order to improve the reactivity.

이상 설명한 바와 같이 본 발명에 의하면 제강 슬래그로부터 Fe를 효율적으로 회수할 수 있다. INDUSTRIAL APPLICABILITY As described above, according to the present invention, Fe can efficiently be recovered from steelmaking slag.

또 제강 슬래그로부터 고부가가치 주조용 소재인 Fe-P 합금을 생산할 수 있다. In addition, Fe-P alloy, which is a material for high value-added casting, can be produced from steelmaking slag.

도 1은 본 발명의 한 실시예에 사용된 실험장치를 개략적으로 나타내는 도면이다.
도 2는 본 발명의 한 실시예에서 슬래그를 준비하는 과정을 나타내는 도면이다.
도 3은 본 발명의 여러 실시예에서 사용되는 펠릿 환원제를 나타내는 도면이다.
도 4 내지 도 8은 본 발명의 실시예에서 각각 Charge 1 내지 Charge 5의 경우에 대한 Fe 회수 실험 결과를 나타내는 도면이다.
도 9는 각 Charge의 경우에 따른 Fe 회수율을 나타낸 그래프이다. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic representation of an experimental apparatus used in an embodiment of the present invention.
2 is a view showing a process of preparing slag in an embodiment of the present invention.
Figure 3 is a drawing of a pellet reducing agent used in various embodiments of the present invention.
FIGS. 4 to 8 are graphs showing results of Fe recovery test for Charge 1 to Charge 5, respectively, in the embodiment of the present invention.
FIG. 9 is a graph showing the Fe recovery rate in the case of each charge.

이하에서는, 첨부한 도면을 참조하여 본 발명의 장점, 특징 및 바람직한 실시예에 대하여 상세히 설명한다.Hereinafter, advantages, features, and preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

도 1에 나타난 것과 같은 실험 장치와 아래와 같은 조건에서 슬래그로부터 Fe를 환원하는 실험을 실시하였다. An experimental apparatus as shown in Fig. 1 and an experiment for reducing Fe from slag were conducted under the following conditions.

Slag: 전기로 slag(100g)Slag: electric slag (100g)

전해철: 70gElectrolytic iron: 70g

온도: 1550℃Temperature: 1550 ℃

분위기: ArAtmosphere: Ar

샘플 채취 시간: 0, 5, 10, 30, 60 minSample collection time: 0, 5, 10, 30, 60 min

도가니: Fused MgO Crucible: Fused MgO

구체적으로, 먼저 표 1과 같은 조성의 슬래그를 준비하였다. Specifically, slag having the composition shown in Table 1 was first prepared.

Figure pat00001
Figure pat00001

슬래그는, 도 2에 나타난 것과 같이, 파쇄, 1차 분리, 최종 분리를 거쳐 입도 1.70mm 내지 3.35mm의 분말로 만들었다. The slag was made into a powder having a particle size of 1.70 mm to 3.35 mm through crushing, primary separation and final separation as shown in Fig.

이와 같이 준비된 슬래그를 도 1의 장치에서 용융하였다. The thus prepared slag was melted in the apparatus of Fig.

이어서, 용융된 슬래그에 환원제로서 도 3과 같은 다양한 펠릿을 투입하여(Charge 1 내지 Charge 5) Fe 회수율을 측정하는 실험을 수행하였다. Next, various pellets as shown in FIG. 3 were charged as a reducing agent (Charge 1 to Charge 5) into the molten slag to conduct experiments to measure the Fe recovery rate.

도 4 내지 도 8은 각각 Charge 1 내지 Charge 5의 경우에 대한 실험 결과를 나타내는 도면이다. 4 to 8 are graphs showing experimental results for Charge 1 to Charge 5, respectively.

도 4의 Charge 1은 C만을 사용하여 FeO를 환원한 경우의 결과이다. Charge 1 in FIG. 4 is the result when FeO is reduced using only C. FIG.

환원 반응은 아래와 같다.The reduction reaction is as follows.

FeO + C → Fe+ COFeO + C? Fe + CO

CO 가스로 인한 슬래그 포밍(slag foaming)이 발생하였다.Slag foaming due to CO gas occurred.

펠렛 환원제 일부가 잔류하였는바, 반응시간이 부족했음을 보여준다. Part of the pellet reductant remained, indicating that the reaction time was short.

도 5의 Charge 2는 C에 의해 75%, Al에 의해 25%의 FeO가 Fe로 환원된 경우의 결과이다. Charge 2 in FIG. 5 is a result when FeO is reduced to Fe by 75% by C and by 25% by Al.

이 경우 환원 반응은 아래와 같은 복합 반응이다.In this case, the reduction reaction is a complex reaction as follows.

[FeO(l) + C(s) → Fe(l)+ CO(g)][FeO (l) + C (s)? Fe (l) + CO (g)]

[3FeO(ㅣ) + 2Al(s) → 3Fe(l)+ Al2O3(l)][3FeO (l) + 2Al (s)? 3Fe (l) + Al2O3 (l)]

이 경우도 펠렛 환원제 일부가 잔류하였는바, 반응시간이 부족했음을 보여준다. 슬래그 포밍도 발생하였다. In this case too, a part of the pellet reducing agent remained, indicating that the reaction time was short. Slag foaming also occurred.

도 6의 Charge 3은 C에 의해 50%, Al에 의해 50%의 FeO가 Fe로 환원된 경우의 결과이다. Charge 3 in Fig. 6 is the result when FeO is reduced to Fe by 50% by C and 50% by Al.

환원 반응은 아래와 같은 복합 반응이다.The reduction reaction is a complex reaction as shown below.

[FeO(l) + C(s) → Fe(l)+ CO(g)][FeO (l) + C (s)? Fe (l) + CO (g)]

[3FeO(ㅣ) + 2Al(s) → 3Fe(l)+ Al2O3(l)][3FeO (l) + 2Al (s)? 3Fe (l) + Al2O3 (l)]

이 경우도 펠렛 환원제 일부가 잔류하였는바, 반응시간이 부족했음을 보여준다. 슬래그 포밍도 발생하였다. In this case too, a part of the pellet reducing agent remained, indicating that the reaction time was short. Slag foaming also occurred.

도 7의 Charge 4는 C에 의해 25%, Al에 의해 75%의 FeO가 Fe로 환원된 경우의 결과이다. Charge 4 in Fig. 7 is a result when FeO is reduced to Fe by 25% by C and by 75% by Al.

환원 반응은 아래와 같은 복합 반응이다. The reduction reaction is a complex reaction as shown below.

[FeO(l) + C(s) → Fe(l)+ CO(g)][FeO (l) + C (s)? Fe (l) + CO (g)]

[3FeO(ㅣ) + 2Al(s) → 3Fe(l)+ Al2O3(l)][3FeO (l) + 2Al (s)? 3Fe (l) + Al2O3 (l)]

이 경우에는 잔류 펠렛은 나타나지 않았으며, 슬래그 포밍도 발생하지 않았다. In this case, the residual pellets did not appear and no slag foaming occurred.

도 8의 Charge 5는 Al만에 의해 FeO가 Fe로 환원된 경우의 결과이다. Charge 5 in Fig. 8 is a result when FeO is reduced to Fe by Al alone.

환원 반응은 아래와 같다.The reduction reaction is as follows.

3FeO(ㅣ) + 2Al(s) → 3Fe(l)+ Al2O3(l) 3FeO (l) + 2Al (s) - > 3Fe (l) + Al2O3 (l)

이 경우는 폭발성 반응이 일어났으며, 잔류 펠렛이나 슬래그 포밍은 나타나지 않았다. In this case, an explosive reaction occurred and no residual pellets or slag forming occurred.

표 2에 각각의 차지에 대한 Fe 회수량과 회수율을 나타내었다.Table 2 shows the Fe recovery and recovery rates for each charge.

Charge 1Charge 1 Charge 2Charge 2 Charge 3Charge 3 Charge 4Charge 4 Charge 5Charge 5 환원제 PelletReducing agent Pellet C: 100C: 100 C: 25/Al: 75C: 25 / Al: 75 C: 50/Al: 50C: 50 / Al: 50 C: 25/Al: 75C: 25 / Al: 75 Al: 100Al: 100 회수 FeRecovery Fe 1.60g1.60 g 5.90g5.90 g 3.49g3.49 g 8.05g8.05 g 13.4713.47 회수율Recovery rate 10.32%10.32% 38.06%38.06% 22.51%22.51% 51.93%51.93% 86.90%86.90%

도 9는 각 Charge의 경우에 따른 Fe 회수율을 나타낸 그래프이다. FIG. 9 is a graph showing the Fe recovery rate in the case of each charge.

Charge 5의 Fe 회수율이 가장 높음을 보여준다. Charge 5 shows the highest Fe recovery.

Claims (6)

고온의 용융 상태 슬래그 내에 환원제를 공급하는 단계;
상기 환원제와 슬래그의 반응을 통해 슬래그 내의 FeO를 Fe로 환원시켜 회수하는 단계를 포함하는 것을 특징으로 하는, Fe 함유 슬래그 중 Fe의 회수 방법.
Supplying a reducing agent into the hot molten slag;
And recovering Fe by reducing the FeO in the slag through the reaction of the reducing agent with the slag and recovering the Fe in the Fe-containing slag.
청구항 1에 있어서,
상기 환원제가 Al 또는 C인 것을 특징으로 하는, Fe 함유 슬래그 중 Fe의 회수 방법.
The method according to claim 1,
Wherein the reducing agent is Al or C. 15. A method for recovering Fe in an Fe-containing slag,
청구항 2에 있어서,
상기 환원제가 펠렛 형태인 것을 특징으로 하는, Fe 함유 슬래그 중 Fe의 회수 방법.
The method of claim 2,
A method for recovering Fe in an Fe-containing slag, wherein the reducing agent is in the form of pellets.
청구항 1에 있어서,
플럭스를 추가로 투입하는 것을 특징으로 하는, Fe 함유 슬래그 중 Fe의 회수 방법.
The method according to claim 1,
Wherein the flux is further added to the Fe-containing slag.
청구항 4에 있어서,
상기 플럭스가 CaF2,CaO, Al 드로스, 레드 머드로 이루어지는 그룹에서 선택되는 어느 하나 이상인 것을 특징으로 하는, Fe 함유 슬래그 중 Fe의 회수 방법.
The method of claim 4,
Wherein the flux is at least one selected from the group consisting of CaF2, CaO, Al dross, and red mud.
청구항 4에 있어서,
상기 플럭스가 펠렛 형태인 것을 특징으로 하는, Fe 함유 슬래그 중 Fe의 회수 방법.The method of claim 4,
A method for recovering Fe in an Fe-containing slag, wherein the flux is in the form of pellets.
KR1020160159190A 2016-11-28 2016-11-28 METHOD FOR RECOVERING Fe FROM CONVERTER SLAG CONTAINING Fe KR20180060095A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109970368A (en) * 2019-04-11 2019-07-05 东北大学 A kind of method that the melting and reducing dealkalize of iron red mud vortex mentions the direct cement of iron

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109970368A (en) * 2019-04-11 2019-07-05 东北大学 A kind of method that the melting and reducing dealkalize of iron red mud vortex mentions the direct cement of iron

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