KR101448147B1 - The recovery method of valuble metals included in slag at copper smelter - Google Patents

The recovery method of valuble metals included in slag at copper smelter Download PDF

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KR101448147B1
KR101448147B1 KR20120100157A KR20120100157A KR101448147B1 KR 101448147 B1 KR101448147 B1 KR 101448147B1 KR 20120100157 A KR20120100157 A KR 20120100157A KR 20120100157 A KR20120100157 A KR 20120100157A KR 101448147 B1 KR101448147 B1 KR 101448147B1
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copper
slag
iron
sulfur
mat
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KR20140034968A (en
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장종신
박수상
김지연
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엘에스니꼬동제련 주식회사
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    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B11/00—Making pig-iron other than in blast furnaces
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0002—Preliminary treatment
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0095—Process control or regulation methods
    • 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

본 발명에 따른 동제련 슬래그에서의 구리 및 철의 회수방법은 동제련 슬래그에 황화철과 카본을 투입하여 중간생성물인 구리매트로 농축시키는 매트농축단계, 상기 매트농축단계를 통해 생성된 매트와 슬래그를 분리하는 분리단계, 상기 매트농축단계를 통해 생성된 구리매트를 동제련 공정으로 회수하여 구리를 회수하는 구리회수단계, 상기 분리단계를 통해 분리된 슬래그에 산소를 주입하여 황을 제거하는 황제거단계 및 상기 황제거단계를 통해 황이 제거된 반응물에 카본을 투입하여 선철을 추출하여 철을 회수하는 철회수단계로 이루어진다.The method for recovering copper and iron in the copper smelting slag according to the present invention comprises the steps of putting iron sulfide and carbon into the copper smelting slag and concentrating the copper smelting slag into an intermediate product copper mat, A copper recovery step of recovering copper by recovering the copper mat produced through the mat concentration step in the copper smelting process, a sulfur recovery step of removing sulfur by injecting oxygen into the slag separated through the separation step And a step of withdrawing iron by extracting pig iron by injecting carbon into the reactant from which sulfur is removed through the sulfur elimination step.

Description

동제련 슬래그에서의 유가금속 회수방법{THE RECOVERY METHOD OF VALUBLE METALS INCLUDED IN SLAG AT COPPER SMELTER}BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recovering valuable metals from copper smelting slag,

본 발명은 동제련 슬래그에서의 유가금속 회수방법에 관한 것으로, 더욱 상세하게는 동제련 슬래그에 함유되어 있는 유가금속인 구리 및 철을 회수하는데 탁월한 효과를 나타내는 동제련 슬래그에서의 유가금속 회수방법에 관한 것이다.
The present invention relates to a method for recovering valuable metals in copper smelting slag, and more particularly, to a method for recovering copper and iron which are valuable metals contained in copper smelting slag, .

본 발명은 동제련 슬래그에서의 유가금속 회수방법에 관한 것으로, 더욱 상세하게는 동제련 슬래그에 함유되어 있는 유가금속인 구리(Copper) 및 철(Iron)을 회수하는데 탁월한 효과를 나타내는 동제련 슬래그에서의 유가금속 회수방법에 관한 것이다.The present invention relates to a method for recovering valuable metals in copper smelting slag, and more particularly, to a copper smelting slag which exhibits an excellent effect in recovering copper and iron which are valuable metals contained in copper smelting slag To a method for recovering valuable metals.

자연계에서 존재하는 금속화합물 중 양전하인 금속의 물리 화학적 성질을 이용하여 철(Fe)을 제외한 구리(Cu), 알루미늄(Al), 아연(Zn) 및 납(Pb) 등을 목적금속으로 채취하는 것을 비철제련이라 하며, 목적금속을 구리(Cu)로 하여 유가 광물 즉, 광석(Ore)에서 채취하는 것을 동제련이라고 칭한다. 슬래그(Slag)는 금속재련업의 고로, 전로 및 용광로 등으로 부터 발생하는 일종의 부산물로 여러가지 유가금속이 포함되어 있다.(Cu), aluminum (Al), zinc (Zn), lead (Pb), and the like excluding the iron (Fe) by using the physicochemical properties of the positive metal among the metal compounds existing in the natural world Nonferrous smelting is called copper smelting. Copper (Cu) is used as a target metal and copper ore (Ore) is used for copper smelting. Slag is a kind of by-product from metal furnace blast furnace, converter and blast furnace, and contains various valuable metals.

환경 및 자원 문제가 세계적 관심사로 대두되고 있는 가운데 국내에서도 각종 부산물의 재활용 기술개발이 다각적으로 이뤄지고 있으며, 특히 동의 제련과정에서 발생되는 슬래그는 다른 산업 부산물과는 달리 천연광석으로부터 특정한 금속을 채취하고 남은 무기질 부산물이라는 점에서 적극적인 기술개발이 요구된다.
As the environmental and resource issues are becoming a global concern, various recycling technologies of various by-products have been developed in Korea. Especially, the slag generated in the copper smelting process, unlike other industrial by-products, Active technology development is required because it is a by-product of minerals.

본 발명의 목적은 동제련 슬래그에 함유되어 있는 유가금속인 구리 및 철을 회수하는데 탁월한 효과를 나타내는 동제련 슬래그에서의 유가금속 회수방법을 제공하는 것이다.
An object of the present invention is to provide a method for recovering valuable metals from copper smelting slag which exhibits an excellent effect in recovering copper and iron which are valuable metals contained in copper smelting slag.

본 발명의 목적은 동제련 슬래그에 황화철과 카본을 투입하여 중간생성물인 구리매트로 농축시키는 매트농축단계, 상기 매트농축단계를 통해 생성된 구리매트와 반응 잔여물인 슬래그로 분리하는 분리단계, 상기 분리단계를 통해 분리된 구리매트를 동제련 공정으로 회수하여 구리를 회수하는 구리회수단계, 상기 분리단계를 통해 분리된 슬래그에 산소를 주입하여 황을 제거하는 황제거단계 및 상기 황제거단계를 통해 황이 제거된 반응물에 카본을 투입하여 선철을 추출하여 철을 회수하는 철회수단계로 이루어지는 것을 특징으로 하는 동제련 슬래그에서의 구리 및 철의 회수방법을 제공함에 의해 달성된다.The object of the present invention is to provide a method for producing a copper alloy mat which comprises the steps of putting iron sulfide and carbon into a copper smelting slag and concentrating it into a copper mat as an intermediate product, A copper recovering step of recovering the copper mats separated through the copper smelting step to recover copper, a step of removing sulfur by injecting oxygen into the slag separated through the separation step, And recovering iron by extracting the pig iron by injecting carbon into the removed reactant. The method of recovering copper and iron in a copper smelting slag according to claim 1,

본 발명의 바람직한 특징에 따르면, 상기 매트농축단계는 동제련 슬래그 100 중량부 대비 황화철 5 내지 30 중량부 및 카본 0.1 내지 10 중량부를 투입하여 중간생성물인 구리매트를 농축시켜 얻는 것을 특징으로 이루어지는 것으로 한다.According to a preferred aspect of the present invention, the mat concentration step is performed by adding 5 to 30 parts by weight of iron sulfide and 0.1 to 10 parts by weight of carbon relative to 100 parts by weight of the copper smelting slag to concentrate the copper mat as the intermediate product .

본 발명의 더 바람직한 특징에 따르면, 상기 황제거단계는 상기 분리단계를 통해 분리된 슬래그 100 중량부 대비 1 내지 7 L의 산소를 주입하고 1000 내지 1500℃의 온도에서 반응시켜 황을 제거하는 것을 특징으로 이루어지는 것으로 한다.According to a more preferred feature of the present invention, the sulfur elimination step is carried out by introducing 1 to 7 L of oxygen relative to 100 parts by weight of slag separated through the separation step, and removing sulfur by reacting at a temperature of 1000 to 1500 ° C .

본 발명의 더욱 바람직한 특징에 따르면, 상기 철회수단계는 상기 황제거단계를 통해 황이 제거된 반응물 100 중량부 대비 카본 1 내지 10 중량부를 투입하여 1200 내지 1800℃의 온도에서 반응시키고 선철을 추출하여 철을 회수하는 것을 특징으로 이루어지는 것으로 한다.
According to a more preferred feature of the present invention, the step of withdrawing is performed by adding 1 to 10 parts by weight of carbon relative to 100 parts by weight of the sulfur-removed reactant through the sulfur elimination step, reacting at a temperature of 1200 to 1800 ° C, Is recovered.

본 발명에 따른 동제련 슬래그에서의 유가금속 회수방법은 동제련 슬래그에 함유되어 있는 유가금속인 구리 및 철의 회수율이 90% 이상의 달하여, 동제련 슬래그에서의 구리 및 철을 회수하는데 있어서 탁월한 효과를 나타낸다.
The method for recovering valuable metals in the copper smelting slag according to the present invention is characterized in that the recovery rate of copper and iron, which are valuable metals contained in the copper smelting slag, reaches 90% or more, which is an excellent effect in recovering copper and iron in the copper smelting slag .

도 1은 본 발명에 따른 동제련 슬래그에서의 유가금속 회수방법에 관한 순서도이다.1 is a flow chart of a method for recovering valuable metals in a copper smelting slag according to the present invention.

이하에는, 본 발명의 바람직한 실시예와 각 성분의 물성을 상세하게 설명하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 상세하게 설명하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.
Hereinafter, preferred embodiments of the present invention and physical properties of the respective components will be described in detail with reference to the accompanying drawings. However, the present invention is not limited thereto, And this does not mean that the technical idea and scope of the present invention are limited.

본 발명에 따른 동제련 슬래그에서의 구리 및 철의 회수방법은 동제련 슬래그에 황화철과 카본을 투입하여 중간생성물인 구리매트로 농축시키는 매트농축단계(S101), 전술한 매트농축단계(S101)를 통해 생성된 구리매트와 반응 잔여물인 슬래그로 분리하는 분리단계(S103), 전술한 분리단계(S103)를 통해 분리된 구리매트를 동제련 공정으로 회수하여 구리를 회수하는 구리회수단계(S105), 전술한 분리단계(S103)를 통해 분리된 반응 잔여물인 슬래그에 산소를 주입하여 황을 제거하는 황제거단계(S105') 및 전술한 황제거단계(S105')를 통해 황이 제거된 반응물에 카본을 투입하여 선철을 추출하여 철을 회수하는 철회수단계(S107)로 이루어진다.The method for recovering copper and iron in the copper smelting slag according to the present invention comprises the steps of: (S101) a step of concentrating a copper smelting slag into a copper mat as an intermediate product by injecting iron sulfide and carbon into the copper smelting slag; (S103) for separating the copper mat produced through the separation step (S103) into slag which is a reaction residue, a copper recovery step (S105) for recovering the copper mat separated through the separation step (S103) The sulfur is removed through the sulfur elimination step S105 'for removing sulfur by injecting oxygen into the slag which is the reaction residue separated through the separation step S103 described above and the sulfur removal step S105' And withdrawing the pig iron to recover the iron (S107).

전술한 매트농축단계(S101)는 동제련 슬래그 100 중량부 대비 황화철(FeS₂) 5 내지 30 중량부 및 카본(C) 0.1 내지 10 중량부를 투입하여 중간생성물인 구리매트(Copper matte)를 농축시켜 얻는 것이 바람직하다.The mat concentration step (S101) described above is performed by adding 5 to 30 parts by weight of iron sulfide (FeS₂) and 0.1 to 10 parts by weight of carbon (C) to 100 parts by weight of copper smelting slag and concentrating the copper matte .

전술한 분리단계(S103)는 전술한 매트농축단계를 통해 생성된 구리매트와 반응 잔여물인 슬래그로 분리하는 단계로, 전술한 매트농축단계를 통해 침전된 구리매트를 제거하여 남은 반응 잔여물인 슬래그를 분리하는 것이 바람직하다.The separation step (S103) is a step of separating the copper mat produced through the above-mentioned mat concentration step and the slag, which is a reaction residue, by removing the precipitated copper mat through the above-mentioned mat concentration step, It is preferable to separate them.

전술한 구리회수단계(S105)는 전술한 분리단계(S103)를 통해 분리된 구리매트를 동제련 공정으로 회수하여 구리를 회수하여 이루어지는 것이 바람직하다.The above-described copper recovery step (S105) is preferably performed by recovering the copper mat separated through the separation step (S103) to copper smelting process to recover copper.

전술한 황제거단계(S105')는 전술한 분리단계를 통해 분리된 슬래그 100 중량부 대비 1 내지 10 L의 산소를 주입하고 1000 내지 1500℃의 온도에서 반응시켜 황(S)을 제거하는 것이 바람직하다.In the above-described sulfur removal step (S105 '), 1 to 10 L of oxygen is injected relative to 100 parts by weight of the slag separated through the separation step described above, and sulfur (S) is removed by reacting at a temperature of 1000 to 1500 ° C Do.

전술한 철회수단계(S107)는 전술한 황제거단계를 통해 황이 제거된 반응물 100 중량부 대비 카본 1 내지 10 중량부를 투입하여 1200 내지 1800℃의 온도에서 반응시키고 선철(Pig-iron)을 추출하여 철을 회수하는 것이 바람직하다.
In the above-described withdrawal number step S107, 1 to 10 parts by weight of carbon is added to 100 parts by weight of the sulfur-removed reactant through the above-described sulfur elimination step, and the reaction is carried out at a temperature of 1200 to 1800 ° C to extract Pig-iron It is desirable to recover iron.

이하에는 본 발명에 따른 동제련 슬래그에서의 유가금속 회수방법을 이용한 동제련 슬래그 중의 함유된 구리 및 철의 회수율과 황제거율의 측정 실험을 진행하여 그 결과를 아래 표 1 내지 3에 나타내었다. (아래 표 1은 황화철의 투입량에 따른 구리의 회수율, 표 2는 산소투입량에 따른 황의 제거율, 표 3은 카본 투입량에 따른 철의 회수율의 결과를 나타내었다.)Hereinafter, the recovery rate and sulfur removal rate of copper and iron contained in the copper smelting slag using the crude metal recovering method in the copper smelting slag according to the present invention were measured, and the results are shown in Tables 1 to 3 below. (Table 1 below shows the recovery rate of copper according to the amount of iron sulfide input, Table 2 shows the removal rate of sulfur according to the amount of oxygen input, and Table 3 shows the recovery rate of iron according to the amount of carbon input.)

<표1><Table 1>

Figure 112012073051058-pat00001
Figure 112012073051058-pat00001

<표2><Table 2>

Figure 112012073051058-pat00002
Figure 112012073051058-pat00002

<표3><Table 3>

Figure 112012073051058-pat00003
Figure 112012073051058-pat00003

상기 표 1 내지 3에서 보는 바와 같이 본 발명에 따른 동제련 슬래그에서의 유가금속 회수방법을 이용한 동제련 슬래그 중의 함유된 구리 및 철의 회수율 측정 실험을 진행한 결과, 상기 표 1에서 보는 바와 같이 구리의 회수율을 살펴보면 황화철을 30g을 투입하였을 때 가장 우수한 회수율을 나타내었으나, 황화철이 과량 투입되어 황성분이 잔존하게 됨으로써 다음 단계인 황제거단계에서 과량의 산소를 필요로 하는 결과를 초래하여, 황화철은 20g을 투입하였을 때 92.4%로 구리회수율이 가장 효율적임을 알 수 있다. 또한 표 2에서 보는 바와 같이 산소 투입량에 따른 황제거율을 살펴보면, 산소를 5.25L 투입하였을 때, 산소 투입량을 최소화하면서 가장 효율적인 96.3%의 황제거율을 나타내는 것을 알 수 있다. 또한, 표 3에서 보는 바와 같이 카본 투입량에 따른 철의 회수율을 살펴보면 카본 투입량이 9g일 때, 90.0%의 가장 효율적인 철의 회수율을 나타내는 것을 알 수 있다.
As shown in Tables 1 to 3, the copper and iron recovery rates of the copper smelting slag using the crude metal recovering method in the copper smelting slag according to the present invention were measured. As a result, as shown in Table 1, The recovery rate was the highest when 30 g of iron sulfide was added. However, excessive iron sulfide was added and the sulfur component remained, which resulted in requiring excessive oxygen in the next step of sulfur removal. It was found that copper recovery rate was the most efficient at 92.4%. In addition, as shown in Table 2, when the amount of oxygen is 5.25 L, the oxygen removal rate is 96.3%, which is the most effective, while minimizing the amount of oxygen input. As can be seen from Table 3, the recovery rate of iron according to the amount of carbon input shows that the most efficient recovery rate of iron is 90.0% when the amount of carbon is 9g.

따라서, 본 발명에 따른 동제련 슬래그에서의 유가금속 회수방법은 동제련 슬래그에 함유되어 있는 유가금속인 구리 및 철의 회수율이 90% 이상의 달하여, 동제련 슬래그에서의 구리 및 철을 회수하는데 있어서 탁월한 효과를 나타낸다.
Accordingly, the method for recovering valuable metals in the copper smelting slag according to the present invention is characterized in that the recovery rate of copper and iron, which are valuable metals contained in the copper smelting slag, reaches 90% or more and excellent in recovering copper and iron in the copper smelting slag Effect.

S101 ; 매트농축단계
S103 ; 분리단계
S105 ; 구리회수단계
S105' ; 황제거단계
S107 ; 철회수단계S101; Mat concentration step
S103; Separation step
S105; Copper recovery phase
S105 ';Emperor's step
S107; Number of retractions

Claims (4)

동제련 슬래그 100 중량부에 황화철 5 내지 30 중량부 및 카본 0.1 내지 10 중량부를 투입하여 중간생성물인 구리매트로 농축시키는 매트농축단계;
상기 매트농축단계를 통해 생성된 구리매트와 반응 잔여물인 슬래그로 분리하는 분리단계;
상기 분리단계를 통해 분리된 구리매트를 동제련 공정으로 회수하여 구리를 회수하는 구리회수단계;
상기 분리단계를 통해 분리된 슬래그 100 중량부 대비 1 내지 10L의 산소를 주입하고 1000 내지 1500℃의 온도에서 반응시켜 황을 제거하는 황제거단계; 및
상기 황제거단계를 통해 황이 제거된 반응물 100 중량부 대비 카본 1 내지 10 중량부를 투입하여 1200 내지 1800℃의 온도에서 반응시켜 선철을 추출하는 철회수단계;로 이루어지는 것을 특징으로 하는 동제련 슬래그에서의 구리 및 철의 회수방법.5 to 30 parts by weight of iron sulfide and 0.1 to 10 parts by weight of carbon are added to 100 parts by weight of the copper smelting slag to concentrate the copper mat as an intermediate product;
A separation step of separating the copper mat produced through the mat concentration step into slag which is a reaction residue;
A copper recovery step of recovering the copper mat separated through the separation step to copper smelting process to recover copper;
Removing the sulfur by adding 1 to 10 L of oxygen per 100 parts by weight of the slag separated through the separation step and reacting at a temperature of 1000 to 1500 ° C; And
And removing the pig iron by adding 1 to 10 parts by weight of carbon relative to 100 parts by weight of the sulfur-eliminated reactant through the sulfur elimination step at a temperature of 1200 to 1800 ° C. Copper and iron recovery methods. 삭제delete 삭제delete 삭제delete
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KR102221329B1 (en) 2020-08-07 2021-02-26 공주대학교 산학협력단 Supplimentary cementitious material manufactured by using the secondary slag generated from valuable metal recovery process for Cupper slag and Zinc slag

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KR100317969B1 (en) 1993-09-30 2002-04-22 쉬에르 피에르 How to Convert Copper or Nickel Matte
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