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KR19980074895A - Recovery method of zinc from low grade waste zinc oxide using organic extractant - Google Patents

Recovery method of zinc from low grade waste zinc oxide using organic extractant Download PDF

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KR19980074895A
KR19980074895A KR1019970010899A KR19970010899A KR19980074895A KR 19980074895 A KR19980074895 A KR 19980074895A KR 1019970010899 A KR1019970010899 A KR 1019970010899A KR 19970010899 A KR19970010899 A KR 19970010899A KR 19980074895 A KR19980074895 A KR 19980074895A
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zinc
zinc oxide
low
grade waste
organic extractant
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주창식
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김희두
우성직물 주식회사
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Abstract

본 발명은 유기추출제를 사용하여 고체 상태로 존재하는 저품위 폐 산화아연 중의 아연 성분만을 유기상으로 용해키시고, 유기상 중의 아연을 산 수용액으로 회수하여 재활용하는 유기추출제를 이용한 저품위 폐 산화아연(zinc ash)으로부터 아연을 회수하는 방법에 관한 것이다.The present invention dissolves the zinc component in the low-grade waste zinc oxide in the solid state using the organic extractant in the organic phase, and the low-grade waste zinc oxide using the organic extractant which recovers and recycles the zinc in the organic phase to the acid aqueous solution. to recover zinc from ash).

종래 폐 산화아연을 재활용하는 습식방법은 산을 사용하여 금속 성분을 모두 침출시키고, 주 불순물인 철 성분과 여타의 불순물을 여러 단계를 거치면서 제거시키는 매우 복잡한 공정을 갖고 있었다.The conventional wet method of recycling waste zinc oxide has a very complicated process of leaching all metal components using acid and removing iron and other impurities, which are the main impurities, in several steps.

본 발명에서는 유기추출제인 D2EHPA(상품명)나 Versatic aicd 911(상품명)을 kerosine(상품명)에 녹인 용액과 저품위 폐 산화아연을 상호 접촉시켜 산화아연만을 용해시키고, 유기상에 녹은 아연과 미세한 분체 상태로 분산되어 존재하는 미 용해 산화아연을 함께 산 수용액으로 회수, 재활용토록한 것이다.In the present invention, a solution of D 2 EHPA (trade name) or Versatic aicd 911 (trade name), which is an organic extractant, is dissolved in kerosine (trade name) and low-grade waste zinc oxide to dissolve only zinc oxide, and zinc dissolved in an organic phase and a fine powder state. The undissolved zinc oxide that is dispersed in the mixture is recovered and recycled together with an aqueous acid solution.

Description

[발명의 명칭][Name of invention]

유기추출제를 이용한 저품위 폐 산화아연으로부터 아연의 회수 방법Recovery method of zinc from low grade waste zinc oxide using organic extractant

[발명의 상세한 설명]Detailed description of the invention

[발명의 목적][Purpose of invention]

본 발명은 유기추출제를 사용하는 단순한 공정으로 저품위 폐 산화아연(zinc ash)으로부터 아연을 회수하여 재활용하는 방법을 제공코자 하는 것이다.The present invention is to provide a method for recovering and recycling zinc from low-grade waste zinc oxide in a simple process using an organic extractant.

[발명이 속하는 기술분야 및 그 분야의 종래기술][Technical field to which the invention belongs and the prior art in that field]

아연 폐기물은 현재 여러 공정에서 다양한 형태로 많은 양이 배출되고 있다. 예를 들면, 도금공장 등에서는 아연 괴(塊)를 고온으로 가열하여 용융상태에서 도금을 수행하고 있으나, 벌크의 상부에 위치한 아연은 공기 중의 산소와 화합하여 폐 산화아연이 발생하게 된다. 폐 산화아연에는 산화되지 않은 아연을 다량 함유하고 있으므로 폐 산화아연(zinc dross)은 용융시켜 재생 아연의 형태로 재활용하고 있으나, 아연의 함량이 상대적으로 낮고 아연의 대부분이 산화적 상태로 존재하는 저품위 폐 산화아연은 그 재활용이 현재까지는 부진한 상태이다.Zinc waste is currently produced in large quantities in various forms in different processes. For example, in a plating factory, the zinc ingot is heated to a high temperature to perform plating in a molten state, but zinc located at the upper part of the bulk is combined with oxygen in the air to generate waste zinc oxide. Since waste zinc oxide contains a large amount of zinc oxide, waste zinc oxide (zinc dross) is melted and recycled in the form of recycled zinc. However, low zinc oxide has a relatively low content of zinc and most of the zinc is in an oxidative state. Waste zinc oxide has been poorly recycled to date.

저품위 폐 산화아연의 재활용에는 몇 가지 방법이 제시되고 있다. 즉 건식법으로는 저품위 폐 산화아연을 탄소와 함께 고온로에서 가열하여 산화아연을 환원시켜 이용하는 방법이 제시되고 있으나, 높은 에너지 비용으로 현재로서는 경제성이 없는 실정이다. 또한 습식법으로 재활용하는 방법은 저품위 폐 산화아연을 황산으로 침출하여, 용액 중에 아연과 함께 용존하는 철 성분을 비롯한 불순물들을 여러 단계를 거쳐 분리 제거한 후, 적당한 형태로 아연을 회수하는 것이다. 그러나 이 방법도 공정이 복잡하여 별다른 관심도 받지 못하고 있는 실정이다.Several methods have been proposed for recycling low-grade waste zinc oxide. In other words, as a dry method, a method of using low-grade waste zinc oxide together with carbon in a high temperature furnace to reduce zinc oxide has been proposed. However, there is currently no economic feasibility at high energy costs. In addition, the method of recycling by wet method is to leach the low-grade waste zinc oxide with sulfuric acid, to separate the impurities including iron components dissolved with zinc in a solution through several steps, and then to recover the zinc in a suitable form. However, this method also does not receive much attention because of the complex process.

[발명이 이루고자 하는 기술적 과제][Technical problem to be achieved]

이에 본 발명에서는 상술한 바와 같이 기존의 폐 산화아연 회수방법이 갖는 공정상의 난제 등을 해결할 수 있는 신규의 아연회수방법을 제공코자 한다.Accordingly, the present invention is to provide a novel zinc recovery method that can solve the process difficulties and the like existing waste zinc oxide recovery method as described above.

[발명의 구성 및 작용][Configuration and Function of Invention]

본 발명은 유기추출제를 사용하여 고체 상태로 존재하는 저품위 폐 산화아연 중의 아연 성분만을 유기상으로 용해시키고, 유기상 중의 아연을 산 수용액을 회수하여 재활용하는 것이다.The present invention uses only an organic extractant to dissolve only the zinc component in the low-grade waste zinc oxide present in the solid state into an organic phase, and recovers and recycles an acid aqueous solution of zinc in the organic phase.

즉, di-2-ethylhexylphosphoric aicd(D2EHPA)-상품명-나-Versatic aicd 911-상품명-을 케로신(kerosine)에 녹인 용액(유기상)과 저품위 페 산화아연을 접촉시키면 산화철은 거의 용해되지 않고 산화아연을 쉽게 용해되었다. 그리고, 아연을 함유하는 유기상을 산 수용액과 접촉시키면 유기상 중에 존재하는 아연은 쉽게 수용액 중으로 이동하였다. 산 수용액 중에 존재하는 아연은 여러 가지 형태로 회수가 가능하므로, 주 불순물이 철 산화물인 저품위 페 산화아연의 재활용에는 di-2-ethylhexylphosphoric aicd(D2EHPA)나 Versatic aicd 911이 매우 적당하다는 것이 밝혀졌다.In other words, iron oxide is hardly dissolved when di-2-ethylhexylphosphoric aicd (D 2 EHPA)-trade name-or-Versatic aicd 911-trade name-is contacted with a solution (organic phase) and low grade zinc oxide. Zinc oxide was easily dissolved. When the organic phase containing zinc was brought into contact with the aqueous acid solution, the zinc present in the organic phase easily migrated into the aqueous solution. Since zinc present in the acid solution can be recovered in various forms, it has been found that di-2-ethylhexylphosphoric aicd (D 2 EHPA) or Versatic aicd 911 is very suitable for recycling low-grade zinc oxide, the main impurities being iron oxide. lost.

이하 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.

유기추출제들은 각기 특정 금속 산화물들을 용해시킬 수 있으므로, 산화철은 용해시키지 않고 산화아연만을 쉽게 용해시키는 유기추출제를 사용하여 철 산화물이 주불순물인 저품위 폐 산화아연 중의 산화아연만을 선별적으로 용해시켜 아연을 회수하는 간단한 공정을 발명하였다.Since organic extractors can dissolve specific metal oxides, organic dispersants that do not dissolve iron oxide easily dissolve only zinc oxide, and selectively dissolve only zinc oxide in low-grade waste zinc oxide where iron oxide is a major impurity. A simple process of recovering zinc has been invented.

유기추출제로 많이 사용되는 di-2-ethylhexylphosphoric aicd(D2EHPA)나 Versatic aicd 911을 kerosin과 혼합하여 30vo1%의 유기상 용액을 만들고, 이 용액과 고상인 저품위 폐 산화아연을 접촉시키면 저품위 폐 산화아연 중의 산화아연 성분은 이들 유기 추출제와 결합하여 유기상 용액 중에서 들어오게 된다. 이때, 주 불순물인 철 산화물은 용해되지 않고 고상에 남아 잔사 여과 과정에서 분리 제거된다. 이 용해 공정의 속도는 비교적 커서, 용해는 약 30분 이내에 완료되었다. 아연을 함유하는 유기상을 산 수용액과 접촉시키면 유기상 중의 아연이 쉽게 산 수용액 중으로 이동하므로, 유기상은 재 사용할 수 있게 되고 산 수용액 중의 아연은 여러 가지 형태로 회수가 가능하게 된다. 유기상의 양이 저품위 폐 산화아연에 비해 상대적으로 적을 경우에는 미 용해된 산화아연이 미세한 입자 상태로 유기상 중에 분산되어 존재하기 때문에 여과를 하여도 제거되지 않았다. 그러나, 유기상에 분산되어 존재하는 산화아연 미세 입자는 산 수용액에 의한 회수공정에서 산에 녹아 수용액 중으로 들어가므로 공정 상에 전혀 문제를 일으키지 않았다.Di-2-ethylhexylphosphoric aicd (D 2 EHPA) or Versatic aicd 911, which is widely used as an organic extractant, is mixed with kerosin to make 30vo1% organic phase solution. The zinc oxide component in combination with these organic extractants enters the organic phase solution. At this time, the iron oxide as the main impurity remains in the solid phase without being dissolved and is separated and removed in the residue filtration process. The rate of this dissolution process was relatively large and dissolution was completed in about 30 minutes. When the organic phase containing zinc is contacted with an aqueous acid solution, the zinc in the organic phase easily moves into the aqueous acid solution, and thus the organic phase can be reused and the zinc in the acid aqueous solution can be recovered in various forms. When the amount of the organic phase was relatively small compared to the low grade waste zinc oxide, undissolved zinc oxide was dispersed in the organic phase in the form of fine particles, and thus was not removed even by filtration. However, the zinc oxide fine particles dispersed in the organic phase were dissolved in the acid into the aqueous solution in the recovery step by the acid aqueous solution and thus did not cause any problem in the process.

따라서, 이 방법은 산을 사용하여 저품위 폐 산화아연을 침출시키는 기존의 공정이 복잡한 정제공정을 거치는데 비하여, 정제 공정이 필요없는 매우 단순한 공정으로 순도가 높은 아연 수용액을 얻을 수 있었다.Therefore, this method was able to obtain a high-purity zinc aqueous solution in a very simple process that does not require a purification process, compared to the conventional process of leaching low-grade waste zinc oxide using acid.

이하 실시예를 통하여 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to the following examples.

[실시예 1]Example 1

D2EHPA를 kerosine에 녹여 그 농도를 30 vol%로 한 용액 200㎖에 저품위 폐 산화아연 10g을 넣고 25℃에서 5시간 동안 교반하면서 산화아연을 충분히 용해시킨 후 잔사를 여과하여 분리한 결과 잔사량은 1.81g이었다.10 g of low-grade waste zinc oxide was added to 200 ml of a solution in which D 2 EHPA was dissolved in kerosine and its concentration was 30 vol%. After stirring for 5 hours at 25 ° C., zinc oxide was sufficiently dissolved, and the residue was filtered and separated. Was 1.81 g.

이 잔사 1.81g에는 저품위 폐 산화아연 중에 산화되지 않고 존재했던 아연 성분도 상당량 확인되었다. 아연을 함유한 D2EHPA 용액을 같은 부피의 180㎖ H2SO4/ℓ 수용액과 함께 교반하면서 아연을 회수하고, 회수액 중 아연을 제외한 각종 금속 이온들(불순물)의 농도를 측정한 결과 다음 표 1과 같은 결과를 얻었다.1.81 g of this residue also showed a significant amount of zinc components that were not oxidized in the low-grade waste zinc oxide. The zinc was recovered by stirring the D 2 EHPA solution containing zinc with an equal volume of 180 ml H 2 SO 4 / l aqueous solution, and the concentration of various metal ions (impurities) except zinc in the recovered solution was measured. The same result as 1 was obtained.

[표1] 회수액 중의 금속 이온 농도(아연 제외)[Table 1] Metal ion concentration in recovered liquid (except zinc)

상기 공정의 반응식은 다음과 같다.The reaction scheme of the process is as follows.

ZnO + 2RH →ZnR2+ H2OZnO + 2RH → ZnR 2 + H 2 O

ZnR2+ H2SO4→ 2RH + ZnSO4 ZnR 2 + H 2 SO 4 → 2RH + ZnSO 4

상기 표에서 보는 바와 같이, 본 공정에서는 두 단계의 단순 공정으로 불순물이 거의 없는 아연 수용액을 얻을 수 있었다.As shown in the above table, in this process, a zinc solution containing almost no impurities was obtained by a simple two-step process.

[실시예 2]Example 2

D2EHPA 용액에 의한 저품위 폐 산화아연 용해공정의 속도를 조사한 결과, D2EHPA의 농도가 30 vo1%인 용액 200㎖에 저품위 폐 산화아연 10g을 25℃에서 용해시키는 경우 약 30분이 경과하면 용해가 완료되었다. 용해가 완료된 D2EHPA 용액 중에는 미용해된 미세 입자가 분산되어 있었으나, 이 미세 입자들을 제거하지 않은 상태에서 산 수용액으로 아연을 회수해도 회수액 중에는 불순물이 거의 없어 이 미세한 입자들은 산화아연 입자이고 이들이 공정에는 전혀 문제를 일으키지 않는다는 것을 알았다.The rate of dissolution of low-grade waste zinc oxide by D 2 EHPA solution was investigated. When 10 g of low-grade waste zinc oxide was dissolved in 200 ml of a solution having a D 2 EHPA concentration of 30 vo1%, it dissolved after about 30 minutes. Has been completed. In the dissolved D 2 EHPA solution, undissolved fine particles were dispersed, but even when zinc was recovered with an aqueous acid solution without removing these fine particles, there were almost no impurities in the recovered solution. I found that it does not cause any problems at all.

[실시예 3]Example 3

아연을 함유한 D2EHPA 용액 중에 존재하는 아연을 황산 수용액을 사용하여 D2EHPA 용액과 황산 수용액의 비, 황산 농도를 달리하면서 아연을 회수한 결과 회수율은 사용된 황산의 총량에 관계함을 알았다.As a result of recovering zinc from the D 2 EHPA solution containing zinc by varying the ratios of sulfuric acid and the ratio of D 2 EHPA solution to sulfuric acid, the recovery rate was found to be related to the total amount of sulfuric acid used. .

[발명의 효과][Effects of the Invention]

이상에서 상세히 살펴 본 바와 같이 본 발명은 유기추출제를 사용하는 정제가 필요없는 단순한 공정으로 저품위 폐 산화아연(zinc ash)으로부터 아연을 회수하여 재활용토록 함으로서 아연의 회수률과 재활용률을 극대화할 수 있는 매우 유용한 발명이다.As described in detail above, the present invention can maximize the recovery and recycling rate of zinc by recovering zinc from low-grade waste zinc oxide (zinc ash) in a simple process that does not require purification using an organic extractant. It is a very useful invention.

Claims (3)

저품위 폐 산화아연에서 아연을 회수함에 있어서;Recovering zinc from low grade spent zinc oxide; 유기추출제로 di-2-ethylhexylphosphoric aicd(D2EHPA)을 사용하여 저품위 폐 산화아연(zinc ash) 중의 아연을 용해시키는 것을 특징으로 하는 유기추출제를 이용한 저품위 폐 산화아연으로부터 아연의 회수 방법.A method for recovering zinc from low-grade waste zinc oxide using an organic extractant, characterized by dissolving zinc in low-grade waste zinc oxide using di-2-ethylhexylphosphoric aicd (D 2 EHPA) as an organic extractant. 제 1 항에 있어서,The method of claim 1, 상기 유기추출제는 Versatic aicd 911을 사용하는 것을 특징으로 하는 유기추출제를 이용한 저품위 폐 산화아연으로부터 아연의 회수 방법.The method of recovering zinc from low-grade waste zinc oxide using an organic extract, characterized in that the organic extractant is Versatic aicd 911. 저품위 폐 산화아연에서 아연을 회수함에 있어서,;Recovering zinc from low grade spent zinc oxide; 용해 공정 중에서 발생하는 여과되지 않는 미세 산화아연 입자들을 포함한 유기상중의 아연을 산 수용액으로 회수하는 것을 특징으로 하는 유기추출제를 이용한 저품위 폐 산화아연으로부터 아연의 회수 방법.A method for recovering zinc from low-grade waste zinc oxide using an organic extractant, characterized by recovering zinc in an organic phase containing unfiltered fine zinc oxide particles generated during the dissolution process.
KR1019970010899A 1997-03-24 1997-03-24 Recovery method of zinc from low grade waste zinc oxide using organic extractant Ceased KR19980074895A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100902401B1 (en) * 2007-09-04 2009-06-11 (주)풍전비철 Powder for smelting zinc containing steel making dust and method for manufacturing the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100902401B1 (en) * 2007-09-04 2009-06-11 (주)풍전비철 Powder for smelting zinc containing steel making dust and method for manufacturing the same

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