KR101414967B1 - Nd Extraction Metod From Rare Earth element - Google Patents

Nd Extraction Metod From Rare Earth element Download PDF

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KR101414967B1
KR101414967B1 KR20120029493A KR20120029493A KR101414967B1 KR 101414967 B1 KR101414967 B1 KR 101414967B1 KR 20120029493 A KR20120029493 A KR 20120029493A KR 20120029493 A KR20120029493 A KR 20120029493A KR 101414967 B1 KR101414967 B1 KR 101414967B1
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rare earth
acid
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KR20130107589A (en
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재길 한
인철 강
용환 김
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한국생산기술연구원
재단법인 인천테크노파크
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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
    • C22B59/00—Obtaining rare earth metals
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    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
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    • H01F1/053—Alloys characterised by their composition containing rare earth metals
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Abstract

본 발명은 Nd를 포함한 희토류 자석으로부터 희토류인 Nd를 추출하는 공정을 제공하고자 하는 것이다.
종래 희토류 자석으로부터 Nd를 추출하는 공정은 공정 속도가 너무 느려 생산성이 매우 나쁘다는 문제를 지녀 산업화하기에는 곤란한 실정으로, 이에 대하여 본 발명은, Nd를 포함한 희토류 자석을 분쇄하여 Mg 용융액에 넣고 가열한 후 형성된 Nd-Mg 합금으로부터 Nd를 신속하게 추출하는 방법을 개발하였다.
본 발명에 따르면, Nd-Mg 합금 단편을 강산으로 용해하고, 이에 시약을 넣어 Nd 착화합물을 침전시켜, 상기 침전을 여과분리하고 가열하여 Nd 산화물을 얻게 하였다. The present invention is intended to provide a process for extracting rare earth Nd from a rare earth magnet containing Nd.
Conventionally, a process for extracting Nd from rare earth magnets has been problematic in that the productivity is very low due to a too slow process speed. In the present invention, rare earth magnets containing Nd are pulverized, put into a Mg melt and heated A method of rapidly extracting Nd from the formed Nd-Mg alloy has been developed.
According to the present invention, an Nd-Mg alloy piece is dissolved in a strong acid, and a reagent is added thereto to precipitate an Nd complex. The precipitate is separated by filtration and heated to obtain an Nd oxide.

Description

희토류 자석으로부터 Ｎｄ를 추출하는 방법{Nd Extraction Metod From Rare Earth element}A method of extracting Nd from a rare earth magnet {Nd Extraction Metod From Rare Earth element}

본 발명은 Nd을 포함한 희토류 자석으로부터 Nd를 추출하는 기술에 관한 것이다.The present invention relates to a technique for extracting Nd from rare earth magnets containing Nd.

최근 희토류 금속에 대한 수요가 높아지면서 자원 무기화 현상이 나타나 이에 대한 보완책으로 희토류 재활용 기술에도 관심과 연구가 높아지고 있다. 희토류 금속에 해당하는 Nd 역시 전기자동차나 하이브리드 전기자동차의 부품, 고성능 모터, 전자부품 등을 만드는데 필요한 원소로 Nd-Fe-B로 구성된 희토류 자석에 포함된 Nd를 추출하여 활용하고자 하는 시도가 이루어지고 있다. Recently, as the demand for rare earth metals has increased, resource mineralization phenomenon has appeared, and research and interest on rare earth recycling technology is increasing as a complementary measure. Nd, which is a rare earth metal, is an attempt to extract Nd contained in a rare earth magnet composed of Nd-Fe-B as an element necessary for making parts for electric vehicles and hybrid electric vehicles, high-performance motors, and electronic components have.

종래, Nd를 포함한 희토류 자석으로부터 Nd를 추출하는 방법으로는, 용출, 크로마토그래피, 침전법, 용매추출법 등이 시도되어 왔지만, 추출량이 극소량에 그치거나, 추출속도가 느려 재활용 산업으로 자리 잡기는 어려운 실정이다. Conventionally, as a method of extracting Nd from rare earth magnets containing Nd, elution, chromatography, precipitation, solvent extraction, and the like have been attempted. However, it is difficult to extract Nd from a rare earth magnet containing Nd, It is true.

따라서 본 발명의 목적은 Nd를 포함한 희토류 자석으로부터 Nd를 높은 생산성으로 추출하는 새로운 방법을 제공하고자 하는 것이다. It is therefore an object of the present invention to provide a novel method for extracting Nd from a rare earth magnet containing Nd with high productivity.

본 발명은, Nd를 포함한 희토류 자석을 분쇄하여 Mg 용융액에 넣고 가열하여 Nd-Mg 합금을 만드는 단계;
Nd-Mg 합금 단편을 산으로 용해하는 단계;
상기 Nd-Mg 합금 단편이 산으로 용해된 용액에 Nd 착화합물을 만들기 위해 옥살산을 시약으로 첨가하는 단계;
시약을 첨가하는 단계에서 생성된 Nd 착화합물 침전을 여과분리하는 단계; 및
상기 여과분리된 Nd 착화합물 침전을 가열하여 Nd 산화물을 얻는 단계;를 포함하는 것을 특징으로 하는 Ｎｄ를 추출하는 방법을 제공할 수 있다.The present invention relates to a method for producing a Nd-Mg alloy, which comprises grinding a rare-earth magnet including Nd, pulverizing it into a Mg melt and heating it to form an Nd-Mg alloy;
Dissolving the Nd-Mg alloy piece in an acid;
Adding oxalic acid as a reagent to form a Nd complex in a solution in which the Nd-Mg alloy fraction is dissolved in an acid;
Separating the Nd complex precipitate formed in the step of adding the reagent by filtration; And
And heating the filtered and isolated Nd complex precipitate to obtain an Nd oxide. The present invention also provides a method for extracting Nd.

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또한, 본 발명은, 상기 산은 염산, 질산, 황산 중 어느 하나를 포함하고, pH 3 이하인 강산임을 특징으로 하는 Ｎｄ를 추출하는 방법을 제공할 수 있다. Also, the present invention provides a method for extracting Nd, wherein the acid comprises any one of hydrochloric acid, nitric acid, and sulfuric acid, and is a strong acid having a pH of 3 or less.

또한, 본 발명은, Nd 착화합물 침전 가열은 대기 중에서 450 내지 850℃에서 하는 것을 특징으로 하는 Ｎｄ를 추출하는 방법을 제공할 수 있다. Further, the present invention can provide a method for extracting Nd, characterized in that Nd complex precipitation heating is performed at 450 to 850 캜 in the air.

본 발명에 따르면, 희토류 자석으로부터 희토류 금속인 Nd를 높은 생산성으로 회수할 수 있다. According to the present invention, it is possible to recover Nd, which is a rare earth metal, from rare earth magnets with high productivity.

즉, 본 발명은 Nd를 착화합물 침전으로 석출시켜 여과 분리함으로써 Nd를 추출할 수 있으므로 매우 간단한 공정으로, 침전 반응 특유의 신속성을 가지고 Nd를 추출한다. That is, the present invention extracts Nd by precipitating Nd by complex precipitation, separating the Nd by filtration, and extracting Nd with a specific rapidity in a very simple process.

도 1은 본 발명에 따라 희토류 자석으로부터 Nd를 추출하는 방법을 단계적으로 나타내는 순서도 이다.
도 2는 본 발명의 바람직한 실시예에서 희토류 자석을 단편으로 분쇄하는 단계를 설명하는 도해도 이다.
도 3은 본 발명의 바람직한 실시예에 대한 전체 공정 순서도 이다.
도 4는 희토류 자석의 조성을 나타내는 테이블도 이다.
도 5는 본 발명의 바람직한 실시예에 의해 추출된 Nd시편의 순도를 나타내는 테이블도 이다.
도 6은 본 발명의 바람직한 실시예에 의해 추출된 Nd시편의 XRD 결과 그래프이다. Fig. 1 is a flowchart showing steps of a method for extracting Nd from a rare-earth magnet according to the present invention.
2 is a view for explaining a step of pulverizing a rare-earth magnet to a piece in the preferred embodiment of the present invention.
Figure 3 is an overall process flow diagram for a preferred embodiment of the present invention.
4 is a table showing the composition of the rare-earth magnet.
5 is a table showing the purity of the Nd specimen extracted by the preferred embodiment of the present invention.
6 is a graph of the XRD result of the Nd specimen extracted by the preferred embodiment of the present invention.

이하, 본 발명의 바람직한 실시예에 대해, 첨부도면을 참조하여 상세히 설명한다.Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

도 1은 본 발명의 Nd 추출방법에서 거치는 단계를 개략적으로 나타내는 순서도 이다. 먼저, 도 2에 도시한 바와 같이, Nd를 포함한 희토류자석을 300 내지 400 ℃, 바람직하게는 380℃ 정도에서 질소 또는 불활성 가스 분위기에서 2 시간 정도 열처리하여 탈자(脫磁)하고, 이를 해머 밀링 또는 볼 밀링 등으로 분쇄하여 Nd를 포함한 단편을 만든다. Fig. 1 is a flowchart schematically showing steps of the Nd extraction method of the present invention. First, as shown in Fig. 2, a rare-earth magnet containing Nd is heat-treated at 300 to 400 DEG C, preferably about 380 DEG C for about 2 hours in a nitrogen or inert gas atmosphere, Ball milling or the like to produce a fragment containing Nd.

다음, 노(爐)에 Mg을 넣고 가열하여 용융시키고, 여기에 Nd를 포함한 단편을 넣는다. 노를 다시 650 내지 850 ℃로 가열하면, 결정질의 Nd-Mg 합금이 얻어진다. Next, Mg is placed in a furnace, heated and melted, and a piece containing Nd is introduced into the furnace. When the furnace is again heated to 650 to 850 캜, a crystalline Nd-Mg alloy is obtained.

상기 결정질의 Nd-Mg 합금은 다시 밀링으로 분쇄하여 단편으로 만들 수도 있으나, 분쇄공정을 생략하고 이하의 공정을 실시할 수도 있다. The crystalline Nd-Mg alloy may be pulverized by milling again to form a piece, but the following process may be carried out by omitting the pulverization process.

상기에서 얻은 Nd-Mg 합금 단편은 강산으로 용해시켜 용액상태로 만든다.The Nd-Mg alloy fragments obtained above are dissolved in strong acid to form a solution state.

사용될 수 있는 강산은 염산, 질산, 황산 중 어느 하나일 수 있으나, 바람직하게는 염산(HCl)을 사용한다.The strong acid which can be used may be any one of hydrochloric acid, nitric acid and sulfuric acid, but preferably hydrochloric acid (HCl) is used.

다음, Nd-Mg 합금 단편이 강산으로 용해된 용액에 시약을 첨가하여 Nd 착화합물을 만든다. 시약으로 바람직한 것으로 옥살산(oxalic acid)을 들 수 있다. 옥살산을 첨가하면, 용액 속에는 Nd를 포함한 착화합물이 생성되어 침전되고, Mg는 이온으로 남게 된다. 이와 같은 침전 반응은 매우 신속하게 일어나므로 생산성이 매우 높아진다. Next, the reagent is added to the solution in which the Nd-Mg alloy piece is dissolved in the strong acid to make the Nd complex. As a reagent, oxalic acid is preferably used. When oxalic acid is added, a complex containing Nd is formed and precipitated in the solution, and Mg remains as an ion. Such a precipitation reaction occurs very quickly, which leads to a high productivity.

따라서, 상기 침전을 여과 분리하는 것으로 Mg으로부터 Nd를 쉽게 분리할 수가 있다. 여과지를 이용하여 여과된 침전물을 대기 중에서 450 내지 850 ℃로 가열하면 Nd를 포함한 착화합물은 Nd 산화물로 바뀌게 되어 이후, 산화물 정제로 Nd를 순도 높게 추출할 수 있게 된다. Therefore, Nd can be easily separated from Mg by separating the precipitate by filtration. When the filtered precipitate is heated to 450 to 850 ° C in the atmosphere, the complex containing Nd is converted into Nd oxide, and then Nd can be extracted with high purity by oxide purification.

도 3은 본 발명의 바람직한 일실시예를 나타내는 전체 공정 순서도 이다.3 is an overall process flowchart showing a preferred embodiment of the present invention.

본 실시예에서는 상기에서 설명한 바와 같이, 희토류 자석의 분쇄 및 Mg과의 용융 후 얻은 Nd-Mg 합금 단편을 염산 용액으로 용해시켜 얻은 용액에 10 중량% 내외의 농도를 갖는 옥살산을 첨가하여 Nd 착화합물 침전을 얻었다. 여과지로 침전을 분리수거하고, 이것을 450 내지 850 ℃로 대기 중에서 열처리하여 Nd 산화물을 얻었다. 상기 시편에는 Nd 산화물 시편에 대한 XRD 분석을 통한 결과를 도 6에 나타내었으며, 이로부터 Nd 산화물이 형성되어 있음을 확인할 수 있었다. In this embodiment, as described above, oxalic acid having a concentration of about 10% by weight or less is added to a solution obtained by dissolving an Nd-Mg alloy piece obtained by pulverizing a rare earth magnet and melting with Mg in a hydrochloric acid solution to form Nd complex precipitation ≪ / RTI > The precipitate was separated and collected with a filter paper, and was heat-treated at 450 to 850 캜 in the air to obtain Nd oxide. The results of XRD analysis of Nd oxide specimens are shown in FIG. 6, which shows that Nd oxides are formed.

본래 희토류 자석 및 이로부터 만든 Nd-Mg시편에 포함된 원소 조성은 도 4에 나타내었으며, 이로부터 본 실시예를 거쳐 얻은 Nd 산화물을 정제한 시편에는 도 5에서와 같이 99.7, 99.8 % 순도의 Nd를 포함하고 있음을 알 수 있어, 본 실시예에 의해 순도 높은 Nd추출이 가능함을 알 수 있었다.
The composition of the rare earth magnets and the Nd-Mg specimen made from the rare earth magnets are shown in FIG. 4, and the specimens obtained by purifying the Nd oxide obtained through this example have Nd of 99.7 and 99.8% purity , And it was found that Nd extraction with high purity can be performed according to the present embodiment.

본 발명의 권리는 위에서 설명된 실시예에 한정되지 않고 청구범위에 기재된 바에 의해 정의되며, 본 발명의 분야에서 통상의 지식을 가진 자가 청구범위에 기재된 권리범위 내에서 다양한 변형과 개작을 할 수 있다는 것은 자명하다.It is to be understood that the invention is not limited to the disclosed embodiment, but is capable of many modifications and variations within the scope of the appended claims. It is self-evident.

도면부호 없음.No reference symbol.

Claims (4)

Nd를 포함한 희토류 자석을 분쇄하여 Mg 용융액에 넣고 가열하여 Nd-Mg 합금을 만드는 단계;
Nd-Mg 합금 단편을 산으로 용해하는 단계;
상기 Nd-Mg 합금 단편이 산으로 용해된 용액에 Nd 착화합물을 만들기 위해 옥살산을 시약으로 첨가하는 단계;
시약을 첨가하는 단계에서 생성된 Nd 착화합물 침전을 여과분리하는 단계; 및
상기 여과분리된 Nd 착화합물 침전을 가열하여 Nd 산화물을 얻는 단계;를 포함하는 것을 특징으로 하는 Ｎｄ를 추출하는 방법.Pulverizing a rare-earth magnet including Nd into a Mg melt and heating it to form an Nd-Mg alloy;
Dissolving the Nd-Mg alloy piece in an acid;
Adding oxalic acid as a reagent to form a Nd complex in a solution in which the Nd-Mg alloy fraction is dissolved in an acid;
Separating the Nd complex precipitate formed in the step of adding the reagent by filtration; And
And heating the filtered and separated Nd complex precipitate to obtain an Nd oxide. 제1항에 있어서, 상기 산은 염산, 질산, 황산 중 어느 하나를 포함하고, pH 3 이하인 강산임을 특징으로 하는 Ｎｄ를 추출하는 방법. The method of extracting Nd according to claim 1, wherein the acid is any one of hydrochloric acid, nitric acid, and sulfuric acid, and is a strong acid having a pH of 3 or less. 삭제delete 제1항에 있어서, Nd 착화합물 침전 가열은 대기 중에서 450 내지 850℃에서 하는 것을 특징으로 하는 Ｎｄ를 추출하는 방법.


The method of claim 1, wherein the Nd complex precipitation heating is performed at 450 to 850 ° C in the atmosphere.


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JPH11319752A (en) * 1998-05-12 1999-11-24 Sumitomo Metal Mining Co Ltd Recovery of valued composition from rare earth element-containing substance and alloy powder obtained thereby
KR100578712B1 (en) 2004-11-04 2006-05-12 한국지질자원연구원 Recovery of Neodymium from NdFeB Oxidation-Roasted Scrap by Acetic Acid Leaching
JP2009249674A (en) * 2008-04-04 2009-10-29 Shin Etsu Chem Co Ltd Method for recovering rare-earth element

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JPH11319752A (en) * 1998-05-12 1999-11-24 Sumitomo Metal Mining Co Ltd Recovery of valued composition from rare earth element-containing substance and alloy powder obtained thereby
KR100578712B1 (en) 2004-11-04 2006-05-12 한국지질자원연구원 Recovery of Neodymium from NdFeB Oxidation-Roasted Scrap by Acetic Acid Leaching
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