KR101089519B1 - Method for Producing CMB Catalyst recycled with Lithium Ion Battery and Ternary Cathode Materials - Google Patents
Method for Producing CMB Catalyst recycled with Lithium Ion Battery and Ternary Cathode Materials Download PDFInfo
- Publication number
- KR101089519B1 KR101089519B1 KR20090116570A KR20090116570A KR101089519B1 KR 101089519 B1 KR101089519 B1 KR 101089519B1 KR 20090116570 A KR20090116570 A KR 20090116570A KR 20090116570 A KR20090116570 A KR 20090116570A KR 101089519 B1 KR101089519 B1 KR 101089519B1
- Authority
- KR
- South Korea
- Prior art keywords
- solvent
- manganese
- solution
- cobalt
- extraction
- Prior art date
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/68—Liquid treating or treating in liquid phase, e.g. dissolved or suspended including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
본 발명은 폐전지 물질로부터의 코발트 및 망간의 회수방법, 및 이를 이용한 Co-Mn-Br 액상촉매의 제조방법에 관한 것으로, 보다 상세하게는, 폐리튬이온전지 분말 및 3원계 양극활물질 제조과정에서 발생하는 스크랩에 대해 황산환원침출, 중화적정, 고액분리, 용매추출 및 수세척 공정을 순차적으로 적용시켜 코발트 및 망간을 회수하는 것을 특징으로 하는 코발트 및 망간의 회수방법, 및 상기 방법으로 얻어진 코발트 및 망간을 포함하는 추출물을 이용하여 Co-Mn-Br 액상촉매를 제조하는 방법에 관한 것이다.The present invention relates to a method for recovering cobalt and manganese from waste battery materials, and to a method for producing a Co-Mn-Br liquid catalyst using the same, more specifically, in the process of manufacturing waste lithium ion battery powder and ternary cathode active material. Cobalt and manganese recovery method characterized by recovering cobalt and manganese by sequentially applying a sulfuric acid reduction leaching, neutralization titration, solid-liquid separation, solvent extraction and water washing process to the generated scrap, and the cobalt and It relates to a method for preparing a Co-Mn-Br liquid catalyst using an extract containing manganese.
본 발명에 따르면, 폐리튬이온전지 및 3원계 양극활물질 제조과정에서 발생하는 부산물로부터 코발트 및 망간을 회수하되, 불순물의 제거율 및 회수율을 높임으로써, 고순도의 코발트 및 망간을 회수할 수 있으며, 상기 회수액은 CMB 액상촉매 제조의 원료로 사용하는데 유용하다.According to the present invention, while recovering cobalt and manganese from by-products generated in the process of manufacturing a lithium ion battery and a ternary positive electrode active material, by increasing the removal rate and recovery of impurities, high-purity cobalt and manganese can be recovered, the recovery solution Is useful as a raw material for the production of CMB liquid catalysts.
폐리튬이온전지, 폐 3원계 양극활물질, 코발트, 망간, CMB 액상촉매 Waste Lithium Ion Battery, Waste Ternary Cathode Active Material, Cobalt, Manganese, CMB Liquid Catalyst
Description
본 발명은 폐전지 물질로부터의 코발트 및 망간의 회수방법, 및 이를 이용한 Co-Mn-Br 액상촉매의 제조방법에 관한 것으로, 보다 상세하게는, 폐리튬이온전지 분말 및 3원계 양극활물질 제조과정에서 발생하는 스크랩에 대해 황산환원침출, 중화적정, 고액분리, 용매추출 및 수세척 공정을 순차적으로 적용시켜 코발트 및 망간을 회수하는 것을 특징으로 하는 코발트 및 망간의 회수방법, 및 상기 방법으로 얻어진 코발트 및 망간을 포함하는 추출물을 이용하여 Co-Mn-Br 액상촉매를 제조하는 방법에 관한 것이다.The present invention relates to a method for recovering cobalt and manganese from waste battery materials, and to a method for producing a Co-Mn-Br liquid catalyst using the same, more specifically, in the process of manufacturing waste lithium ion battery powder and ternary cathode active material. Cobalt and manganese recovery method characterized by recovering cobalt and manganese by sequentially applying a sulfuric acid reduction leaching, neutralization titration, solid-liquid separation, solvent extraction and water washing process to the generated scrap, and the cobalt and It relates to a method for preparing a Co-Mn-Br liquid catalyst using an extract containing manganese.
리튬전지 중 최근에 들어 그 사용량이 급증하고 있는 리튬이차전지는 양극(cathod), 음극(anode), 유기전해질(organic electrolyte) 및 유기분리막(organic separator)으로 구성되어 있다. 그리고, 양극 활물질(active materials)로는 가역성이 우수하고, 낮은 자가방전율, 고용량 및 고에너지밀도를 가지며, 합성이 용이한 리튬코발트 산화물이 상용화되어 있다.Lithium secondary batteries, which have recently increased in usage among lithium batteries, are composed of a cathode, an anode, an organic electrolyte, and an organic separator. In addition, lithium cobalt oxide, which has excellent reversibility, low self discharge rate, high capacity and high energy density, and is easily synthesized, is commercially available as a positive electrode active material.
특히, 리튬이온전지는 경량성으로 인하여 소형 휴대장비의 동력원으로 많이 사용되고 있으며, 최근에는 이동통신 단말기의 폭발적인 증가로 그 수요도 이에 비례하여 증가하고 있다. 또한, 리튬이온전지의 수요가 증가하는 만큼 폐리튬이온전지의 발생량도 급증하고 있는 추세이다.In particular, lithium-ion batteries are widely used as a power source for small portable devices due to their light weight, and in recent years, demand for them has increased in proportion to the explosion of mobile communication terminals. In addition, as the demand for lithium ion batteries increases, the amount of generated lithium ion batteries is also rapidly increasing.
이러한 폐리튬이온전지는 성상이 간단하고 양극활물질로서 비교적 고가인 리튬과 코발트 등의 유가금속이 다량 함유되어 있어 경제적인 가치가 있는 폐자원으로 인식되어 재활용이 요구된다. 그러나, 양극활물질로서 리튬코발트 산화물을 채택한 리튬이온전지의 경우에는 코발트나 리튬과 같은 유가금속이 재활용되어야하고, 리튬이온전지의 효율적 재활용을 위해서는 유가금속의 효율적인 회수뿐만 아니라 폐리튬전지의 재활용 공정 중에서 발생되는 유해폐기물도 적절히 처리하여야만 한다.This waste lithium ion battery is simple in appearance and contains a large amount of valuable metals such as lithium and cobalt, which are relatively expensive as a cathode active material, and thus, it is recognized as an economically valuable waste resource and requires recycling. However, in the case of lithium ion batteries employing lithium cobalt oxide as a positive electrode active material, valuable metals such as cobalt and lithium should be recycled, and for efficient recycling of lithium ion batteries, not only efficient recovery of valuable metals but also recycling of waste lithium batteries Hazardous wastes generated should be properly disposed of.
특히, 폐리튬이온전지를 기계적으로 처리하는 방법 중에 금속리튬은 수분과 격렬하게 반응하면서 산화되므로 매우 위험할 수 있어 폐리튬이온전지로부터 코발트를 효율적으로 회수하기 위해서는 안정적인 기계적 처리 및 유해성분을 최소화시키는 것이 중요하다.In particular, during the mechanical treatment of waste lithium ion batteries, metal lithium is oxidized while reacting violently with moisture, which can be very dangerous. Therefore, in order to efficiently recover cobalt from waste lithium ion batteries, it is necessary to provide stable mechanical treatment and minimize harmful components It is important.
현재 리튬이온전지의 양극활물질의 상용화 트렌드는 LiCoO2로부터 3원계 양극활물질로 이동 중에 있으며, 특히 리튬이온전지의 용도가 대형화, 다양화됨에 따 라 (하이브리드 자동차, 전기자동차, 로봇, 에너지 저장용 등) 3원계 양극활물질을 이용한 리튬이온전지의 수요가 기하급수적으로 증가될 것으로 예측됨에 따라, 이에 상응하는 재활용 기술의 개발이 요구되고 있다.Currently, the commercialization trend of cathode active materials in lithium ion batteries is moving from LiCoO 2 to ternary cathode active materials. Especially, as the use of lithium ion batteries becomes larger and more diversified (hybrid cars, electric cars, robots, energy storage, etc.) As the demand for lithium ion batteries using ternary cathode active materials is expected to increase exponentially, development of corresponding recycling technologies is required.
CMB 액상촉매는 Co-Mn-Br로 이루어진 촉매로서 석유화학제품 중 하나인 파라자일렌(Para-Xylene)을 산화반응시켜 TPA(Terephthalic Acid)를 제조하는 공정의 촉매로 이용되고 있다. 또한 TPA는 우리 생활과 밀접한 폴리에스테르 섬유, PET(Polyethylene Terephthalate)병, 필름, 도료, 타이어코드의 원료가 되며 한국은 TPA 주요 생산국으로 2006년 국내 TPA 생산량은 550만톤으로 세계 TPA 생산 능력(2,600만톤)의 21% 정도를 차지하고 있어, CMB 촉매 시장도 매우 거대하다. 따라서 상기 공정에서 폐기되는 Co와 Mn을 포함하는 폐기물로부터 Co와 Mn을 회수하여 CMB 촉매를 제조함으로서 경제적으로 CMB 촉매를 제조할 수 있다.CMB liquid catalyst is a catalyst composed of Co-Mn-Br, and is used as a catalyst for producing TPA (Terephthalic Acid) by oxidizing para-xylene, one of petrochemical products. In addition, TPA becomes a raw material for polyester fiber, PET (Polyethylene Terephthalate) bottles, films, paints, and tire cords that are closely related to our lives. Korea is a major producer of TPA. In 2006, domestic TPA production amounted to 5.5 million tons. The market for CMB catalysts is huge. Therefore, by recovering Co and Mn from the waste containing Co and Mn discarded in the process, it is possible to economically produce a CMB catalyst.
이에, 본 발명자들은 폐리튬이온전지 및 3원계 양극활물질 제조과정에서 발생하는 스크랩으로부터 효율적인 코발트 및 망간 회수방법을 개발하고자 예의 노력한 결과, 상기 시료를 대상으로 황산환원침출, 불순물 제거(중화적정 및 고액분리) 및 용매추출 및 수세척 공정을 순차적으로 적용시킬 경우, 불순물이 제거된 고순도의 코발트 및 망간을 회수하였으며, 또한 이를 이용하여 CMB 액상촉매를 제조할 수 있다는 것을 확인하고, 본 발명을 완성하게 되었다. Accordingly, the present inventors have made diligent efforts to develop an efficient cobalt and manganese recovery method from scrap generated during the production of waste lithium ion batteries and ternary cathode active materials. When the separation) and solvent extraction and water washing processes were sequentially applied, it was confirmed that the high-purity cobalt and manganese from which impurities were removed were recovered, and that the CMB liquid catalyst could be prepared using the same, thereby completing the present invention. It became.
본 발명의 목적은 폐리튬이온전지 및 3원계 양극활물질 제조과정에서 발생하는 스크랩으로부터 코발트 및 망간의 회수방법 및 상기 방법으로 얻어진 코발트 및 망간을 포함하는 추출액을 사용한 Co-Mn-Br 액상촉매의 제조방법을 제공하는데 있다.An object of the present invention is to prepare a Co-Mn-Br liquid catalyst using a method for recovering cobalt and manganese from scrap generated during the production of waste lithium ion batteries and ternary cathode active materials and extracts containing cobalt and manganese obtained by the above method. To provide a method.
상기 목적을 달성하기 위하여, 본 발명은 (a) 폐전지 물질에 대해 황산과 환원제를 사용하여 침출시키는 단계; (b) 상기 (a) 단계에서 수득한 침출용액을 중화적정하여 불순물을 제거하는 단계; (c) 상기 (b) 단계에서 수득한 침출용액을 용액과 잔사로 고액분리하는 단계; (d) 상기 (c) 단계에서 고액분리된 용액에 용매를 가하여 추출하는 단계; 및 (e) 상기 (d) 단계에서 수득된 추출액을 수세척하는 단계를 포함하는 코발트 및 망간의 회수방법을 제공한다.In order to achieve the above object, the present invention comprises the steps of: (a) leaching with respect to the spent battery material using sulfuric acid and a reducing agent; (b) neutralizing the leaching solution obtained in step (a) to remove impurities; (c) solid-liquid separation of the leaching solution obtained in step (b) into a solution and a residue; (d) extracting by adding a solvent to the solution liquid-separated in step (c); And (e) provides a method for recovering cobalt and manganese comprising the step of washing the extract obtained in step (d).
본 발명은 또한, (a) 상기 코발트 및 망간의 회수방법에서 수득된 추출액에 HBr 용액을 첨가하고, 역추출하여 Co-Mn-Br 탈거용액를 수득하는 단계; 및 (b) 상기 Co-Mn-Br 탈거용액에 코발트염 및 망간염을 첨가하여 적정 농도를 맞추는 단계를 포함하는 폐전지 물질로부터 회수한 코발트 및 망간을 이용한 Co-Mn-Br 액상촉매를 제조하는 방법을 제공한다.The present invention also comprises the steps of: (a) adding a HBr solution to the extract obtained in the recovery method of cobalt and manganese, back extraction to obtain a Co-Mn-Br stripping solution; And (b) adding a cobalt salt and a manganese salt to the Co-Mn-Br stripping solution to adjust an appropriate concentration to prepare a Co-Mn-Br liquid catalyst using cobalt and manganese recovered from a spent battery material. Provide a method.
본 발명에 따르면, 폐리튬이온전지 및 3원계 양극활물질 제조과정에서 발생하는 스크랩으로부터 코발트 및 망간을 회수하되, 불순물의 제거율 및 회수율을 높임으로써, 고순도의 코발트 및 망간을 회수할 수 있으며, 상기 회수액은 CMB 액상 촉매 제조의 원료로 사용하는데 유용하다.According to the present invention, while recovering cobalt and manganese from scrap generated during the production of waste lithium ion batteries and ternary cathode active materials, by increasing the removal rate and recovery of impurities, high-purity cobalt and manganese can be recovered, the recovery solution Is useful as a raw material for the production of CMB liquid catalysts.
본 발명은 일 관점에서, (a) 폐전지 물질에 대해 황산과 환원제를 사용하여 침출시키는 단계; (b) 상기 (a) 단계에서 수득한 침출용액을 중화적정하여 불순물을 제거하는 단계; (c) 상기 (b) 단계에서 수득한 침출용액을 용액과 잔사로 고액분리하는 단계; (d) 상기 (c) 단계에서 고액분리된 용액에 용매를 가하여 추출하는 단계; 및 (e) 상기 (d) 단계에서 수득된 추출액을 수세척하는 단계를 포함하는 코발트 및 망간의 회수방법에 관한 것이다.The present invention in one aspect, (a) leaching with respect to the spent battery material using sulfuric acid and a reducing agent; (b) neutralizing the leaching solution obtained in step (a) to remove impurities; (c) solid-liquid separation of the leaching solution obtained in step (b) into a solution and a residue; (d) extracting by adding a solvent to the solution liquid-separated in step (c); And (e) relates to a method for recovering cobalt and manganese comprising the step of washing the extract obtained in step (d).
본 발명에서, 상기 폐전지 물질은 폐리튬이온전지 및 3원계 양극활물질 제조과정에서 발생하는 스크랩일 수 있다.In the present invention, the waste battery material may be scrap generated in the process of manufacturing the waste lithium ion battery and the ternary cathode active material.
본 발명에서, 상기 폐리튬이온전지는 분말상태일 수 있으며, 본 발명의 방법에는 8 mesh 이하의 분말을 사용하는 것이 바람직하다.In the present invention, the waste lithium ion battery may be in a powder state, it is preferable to use a powder of 8 mesh or less in the method of the present invention.
상기 폐리튬이온전지 분말은 본 발명자의 선행특허인 한국등록특허 제860972호의 물리적 처리 방법으로 수득할 수 있다.The waste lithium ion battery powder may be obtained by a physical treatment method of Korean Patent No. 860972, which is a prior patent of the present inventors.
본 발명에서, 상기 폐전지 물질은 리튬이온전지 양극물질을 제조하는 과정에서 발생되는 양극물질 불합격품 또는 양극활물질 분말 스크랩일 수 있으며, 단순 파분쇄 및 열처리를 통해 분말의 형태로 단체분리하여 3원계 양극활물질 분말로 회수한 것일 수 있다.In the present invention, the waste battery material may be a cathode material rejected material or a cathode active material scrap generated in the process of manufacturing a lithium ion battery cathode material, and ternary cathode by separating into a powder form through simple crushing and heat treatment. It may be recovered as an active material powder.
상기 폐전지 물질에는 코발트, 리튬 등의 유가금속 이외에도 다량의 불순물이 함유되어 있다. 따라서, 상기 (a) 단계에서 폐전지 물질을 황산 및 환원제를 사 용하여 침출시킨 후 수득한 용액으로부터 불순물을 제거하기 위하여, 중화적정을 실시한다.The waste battery material contains a large amount of impurities in addition to valuable metals such as cobalt and lithium. Therefore, in order to remove impurities from the solution obtained after leaching the spent battery material with sulfuric acid and a reducing agent in step (a), neutralization titration is performed.
상기 환원제는 H2, H2S, SO2, FeSO4, 석탄(Coal) 또는 황철광(Pyrite)을 사용할 수 있으며, 바람직하게는 H2O2를사용할 수 있다.The reducing agent may be H 2 , H 2 S, SO 2 , FeSO 4 , coal (pyal) or pyrite (Pyrite), preferably H 2 O 2 may be used.
본 발명에 있어서, 상기 (b)단계의 중화적정은 CaO, Ca(OH)2 및 CaCO3로 구성된 군에서 선택되는 칼슘화합물; NaOH 또는 NH4OH인 알칼리용액; 및 이들의 혼합물로 구성된 군에서 선택되는 물질에 의해 pH 5.5 ~ 6.5로 조정될 수 있으며, 바람직하게는 CaCO3를 사용할 수 있다.In the present invention, the neutralization titration of step (b) is a calcium compound selected from the group consisting of CaO, Ca (OH) 2 and CaCO 3 ; Alkaline solution which is NaOH or NH 4 OH; And it can be adjusted to pH 5.5 ~ 6.5 by a material selected from the group consisting of a mixture thereof, preferably CaCO 3 can be used.
중화적정에 의해 침출용액으로부터 제거될 수 있는 불순물은 Fe, Cu, Al 및 이들의 혼합물로 구성된 군에서 선택되는 것을 특징으로 할 수 있으나, Co, Mn 등과 같이 재활용 가능한 유가금속 이외의 불순물이라면 이에 국한되는 것은 아니다.Impurities that can be removed from the leaching solution by neutralization titration may be selected from the group consisting of Fe, Cu, Al and mixtures thereof, but is limited to impurities other than recyclable valuable metals such as Co and Mn. It doesn't happen.
본 발명에 있어서, 상기 (c)단계의 고액분리는 필터프레스 또는 여과지를 사용하여 용액과 잔여물로 분리할 수 있으며, 상기 고액분리 수단은 당업자에 의해 용이하게 선택될 수 있다.In the present invention, the solid-liquid separation of step (c) can be separated into a solution and a residue using a filter press or filter paper, and the solid-liquid separation means can be easily selected by those skilled in the art.
본 발명에 있어서, 상기 (d)단계에서 사용되는 용매는 di-2-ethyl hexyl phosporic acid계, 2-ethyl hexyl phosponic acid계, mono-2-ethyl hexyl ester계, di-2,4,4-trimethyl penthyl phosphpinic acid계, di-2-ethyl hexyl phospinic acid계, di-2,4,4-trimethyl penthyl dithiophosphpinic acid계 및 di-2,4,4- trimethyl penthyl monothiophosphpinic acid계로 구성된 군에서 선택되는 것을 특징으로 할 수 있으며, 바람직하게는 di-2-ethyl hexyl phosporic acid계 용매를 사용할 수 있다.In the present invention, the solvent used in the step (d) is di-2-ethyl hexyl phosporic acid, 2-ethyl hexyl phosponic acid, mono-2-ethyl hexyl ester, di-2,4,4- trimethyl penthyl phosphpinic acid, di-2-ethyl hexyl phospinic acid, di-2,4,4-trimethyl penthyl dithiophosphpinic acid and di-2,4,4-trimethyl penthyl monothiophosphpinic acid The di-2-ethyl hexyl phosporic acid solvent may be used.
상기 용매는 알칼리용액에 의해 비누화된 것이 바람직하며, 이때, 30 ~ 60% 비누화된 용매를 사용할 수 있으며, 바람직하게는 40 ~ 50% 비누화된 용매를 사용함으로써, 코발트 및 망간의 회수율을 높이고 불순물의 발생은 최소화할 수 있다. 또한, 상기 용매추출 시 사용되는 용매를 비누화하면 용매추출 시 pH 변화를 방지하여 용매추출의 효율을 높일 수 있다. The solvent is preferably saponified by an alkaline solution, and in this case, 30 to 60% saponified solvent may be used, and preferably 40 to 50% saponified solvent may be used to increase the recovery rate of cobalt and manganese and to remove impurities. Occurrence can be minimized. In addition, saponifying the solvent used during the solvent extraction can prevent the pH change during solvent extraction to increase the efficiency of solvent extraction.
예를 들어, 용매추출 시 bis(2,4,4-trimethyl pentyl) phosphinic acid(Cyanex 272, Cytec Inc., USA)를 용매로 사용하여 코발트 및 망간의 추출 반응식 (1)은 다음과 같다. 여기서, X는 Co 또는 Mn 이며, R은 C16H34PO2 -이다.For example, cobalt and manganese extraction scheme (1) using bis (2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272, Cytec Inc., USA) as a solvent is shown below. Wherein X is Co or Mn and R is C 16 H 34 PO 2 — .
X2 + + 2HR ↔ XR2 + 2H+ (1)X 2 + + 2HR ↔ XR 2 + 2H + (1)
이때, 상기 Cyanex 272은 분자량 290, 점도 142cp(25℃), 비중 0.92gm/cc(24℃) 및 순도 85%이며, 분자식은 C16H34PO2H이고, 화학식 I과 같은 구조를 가진다.In this case, the Cyanex 272 has a molecular weight of 290, viscosity 142cp (25 ℃), specific gravity 0.92gm / cc (24 ℃) and purity of 85%, the molecular formula is C 16 H 34 PO 2 H, has the same structure as formula (I).
(I) (I)
반응식 (1)의 반응이 진행됨에 따라 (c) 단계의 고액분리된 용액의 pH가 감소하므로, pH 감소를 억제하기 위하여 용매추출 시 사용하는 용매를 NaOH, NH4OH 등과 같은 알칼리용액을 이용하여 비누화한 다음(반응식 (2)), 용매추출에 사용하였다 (반응식 (3)).As the reaction of Scheme (1) proceeds, the pH of the solid-liquid separated solution of step (c) decreases, so that the solvent used for extracting the solvent using an alkaline solution such as NaOH, NH 4 OH, etc. to suppress the pH decrease. After saponification (Scheme (2)), it was used for solvent extraction (Scheme (3)).
HR + NaOH (or NH4OH) ↔ NaR (or NH4R) + H2X (2)HR + NaOH (or NH 4 OH) ↔ NaR (or NH 4 R) + H 2 X (2)
X2 + + NaR (or NH4R) ↔ XR2 + 2Na+ (or 2NH4 +) (3)X 2 + + NaR (or NH 4 R) ↔ XR 2 + 2Na + (or 2NH 4 + ) (3)
반응식 (2)는 용매의 비누화 과정을 나타낸 반응식으로, 용매의 H+ 이온을 Na+ 또는 NH4 + 이온으로 치환하게 되며, 따라서 반응식 (3)과 같이 용매에 의해 코발트 또는 망간 이온이 추출될 때, 반응식 (2)에서 치환된 Na+ 또는 NH4 + 이온이 용액 상으로 배출되기 때문에 용액의 pH 변화를 방지할 수 있다. Scheme (2) is a reaction formulating the saponification process of the solvent, and the H + ions of the solvent is replaced with Na + or NH 4 + ions, and thus when cobalt or manganese ions are extracted by the solvent as in Scheme (3) In addition, since the Na + or NH 4 + ions substituted in the reaction scheme (2) are discharged into the solution phase, the pH change of the solution can be prevented.
본 발명의 (e) 단계의 수세척 단계는 용매추출된 추출액에 대해 O/A(Organic/Aqueous)의 비율이 10:1 내지 1:10의 조건에서 50℃ 내지 70℃의 증류수를 이용하여 1분 이내로 세척할 수 있으며, 바람직하게는 2:1의 O/A(Organic/Aqueous) 조건에서 60℃의 증류수를 이용하여 세척할 수 있다.The water washing step of step (e) of the present invention is a ratio of O / A (Organic / Aqueous) to the solvent extracted using a distilled water of 50 ℃ to 70 ℃ in a condition of 10: 1 to 1:10 It can be washed within minutes, and preferably, using distilled water at 60 ° C. under O / A (Organic / Aqueous) condition of 2: 1.
본 발명은 다른 관점에서, (a) 상기 코발트 및 망간의 회수방법에서 수득된 추출액에 HBr 용액을 첨가하고, 역추출하여 Co-Mn-Br 탈거용액를 수득하는 단계; 및 (b) 상기 Co-Mn-Br 탈거용액에 코발트염 및 망간염을 첨가하여 적정 농도를 맞추는 단계를 포함하는 폐전지 물질로부터 회수한 코발트 및 망간을 이용한 Co-Mn-Br 액상촉매의 제조방법에 관한 것이다.In another aspect, (a) adding a HBr solution to the extract obtained in the recovery method of cobalt and manganese, back extraction to obtain a Co-Mn-Br stripping solution; And (b) adding cobalt salt and manganese salt to the Co-Mn-Br stripping solution to adjust an appropriate concentration to prepare a Co-Mn-Br liquid catalyst using cobalt and manganese recovered from a waste battery material. It is about.
본 발명에서, 상기 '추출액'은 'Cyanex 272에 의해 추출된 추출용매' 또는 '추출용매'와 혼용될 수 있으며, 상기 Co-Mn-Br 액상촉매 제조방법에 사용되는 상기 추출용매는 코발트와 망간 회수방법의 (d) 단계 또는 (e) 단계에서 수득된 추출액을 개시용매로 사용할 수 있다.In the present invention, the 'extraction solution' may be mixed with 'extraction solvent' or 'extraction solvent' extracted by Cyanex 272, and the extraction solvent used in the Co-Mn-Br liquid catalyst preparation method is cobalt and manganese. The extract obtained in step (d) or step (e) of the recovery method can be used as the starting solvent.
본 발명에서, 상기 폐전지 물질은 폐리튬이온전지 및 3원계 양극활물질 제조과정에서 발생하는 스크랩일 수 있다.In the present invention, the waste battery material may be scrap generated in the process of manufacturing the waste lithium ion battery and the ternary cathode active material.
본 발명에서, 상기 폐리튬이온전지는 분말상태일 수 있으며, 본 발명의 방법에는 8 mesh 이하의 분말을 사용하는 것이 바람직하다. In the present invention, the waste lithium ion battery may be in a powder state, it is preferable to use a powder of 8 mesh or less in the method of the present invention.
본 발명의 역추출(탈거) 단계로 얻어진 Co-Mn-Br 탈거용액은 Co-Mn-Br 액상촉매로 사용하기에는 각 구성분의 함량이 적정량에 미치지 못할 수 있으므로, HBr 용액으로 탈거용액을 수득한 후, 코발트염과 망간염의 적당한 농도를 상기 탈거용액에 추가 혼합하여, Co-Mn-Br 액상촉매의 성분비가 적정함량을 이루도록 할 수 있다.The Co-Mn-Br stripping solution obtained by the reverse extraction (removal) step of the present invention may be used as a Co-Mn-Br liquid catalyst, and thus the content of each component may not reach an appropriate amount. Thereafter, an appropriate concentration of cobalt salt and manganese salt may be further mixed with the stripping solution to achieve a proper content ratio of the Co-Mn-Br liquid catalyst.
상기, (b) 단계에서 코발트염과 망간염은 CoBr2(Cobalt bromide), MnBr2(Maganese Bromide) 및 Mn(OAc)2(maganese acetate)일 수 있으며, Co-Mn-Br 액 상촉매를 제조하기 위하여 탈거용액에 첨가되는 양은 CMB 액상촉매 성분인 Co, Mn 및 Br가 각각 0.51 M, 1.09 M, 1.91 M에 맞도록, 최초 얻어진 Co-Mn-Br 탈거용액 내 코발트, 망간 및 브롬의 함량에 따라 결정될 수 있다.In the step (b), the cobalt salt and manganese salt may be CoBr 2 (Cobalt bromide), MnBr 2 (Maganese Bromide) and Mn (OAc) 2 (maganese acetate), to prepare a Co-Mn-Br liquid catalyst The amount of cobalt, manganese, and bromine in the first Co-Mn-Br stripping solution was added so that the amounts of Co, Mn, and Br, which are CMB liquid catalyst components, were 0.51 M, 1.09 M, and 1.91 M, respectively. Can be determined accordingly.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 요지에 따라 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 당업계에서 통상의 지식을 가진 자에 있어서 자명할 것이다. Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .
실시예Example 1: 용매추출 1: solvent extraction FeedFeed 용액의 제조Preparation of the solution
폐리튬이온전지 분말 및 3원계 양극활물질 제조과정에서 발생되는 스크랩에 대해, 침출액으로서 2 M의 H2SO4 용액과 환원제인 5 ~ 6 vol% H2O2의 혼합용액을 침출액으로 사용하여, 반응온도 60℃, 교반응속도 200~ 250 rpm, 고액비 1:10 및 반응시간 1 hr로 하여, 8 mesh의 폐리튬이온전지 분말 및 3원계 양극활물질 제조과정에서 발생되는 스크랩을 황산환원침출하였다. 2 M of H 2 SO 4 as a leachate for scrap generated during the production of waste lithium ion battery powder and ternary cathode active material 8 mesh using a mixed solution of a solution and a reducing agent of 5 to 6 vol% H 2 O 2 as a leaching solution at a reaction temperature of 60 ° C., a reaction rate of 200 to 250 rpm, a solid solution ratio of 1:10 and a reaction time of 1 hr. Sulfide reduction leaching of the scrap lithium ion battery powder and the ternary cathode active material produced during the production process.
이때, 상기 폐리튬이온전지 분말은 한국등록특허 제860972호에 개시된 바와 같은 물리적 처리에 의해서 수득하였으며, 상기 3원계 양극활물질 제조과정에서 발생되는 스크랩은 단순 파분쇄 및 열처리를 통해 분말의 형태로 단체분리하여 분말 상태로 사용하였다.At this time, the waste lithium ion battery powder was obtained by physical treatment as disclosed in Korean Patent No. 860972, and the scrap generated in the process of manufacturing the ternary cathode active material is formed in the form of powder through simple crushing and heat treatment. Separated and used in powder form.
상기의 황산 침출액을 용매추출 Feed용액으로 제조하기 위하여, 침출액 500mL에 대하여 50% CaCO3 용액 150mL 및 4M NaOH 용액 25mL를 첨가하고, 상온에서 400rpm으로 교반하면서 중화적정한 후, pH를 5.5 ~ 6으로 맞춘 후, 필터프레스로 고액분리하여, 불순물이 포함된 잔여물을 제거하고 용매추출 Feed 용액을 제조하였으며, 최종적으로 침출액의 pH조절에 의해 얻어진 용매추출 Feed 용액의 성분 분석을 한 결과, 불순물인 Cu, Fe, Al가 완전히 제거된 것을 확인할 수 있었다(표 1).In order to prepare the sulfuric acid leaching solution as a solvent extraction feed solution, 150 mL of 50% CaCO 3 solution and 25 mL of 4M NaOH solution were added to 500 mL of the leaching solution, neutralized and titrated with stirring at 400 rpm at room temperature, and then the pH was adjusted to 5.5-6. Then, the solid-liquid separation was carried out by a filter press to remove residues containing impurities and to prepare a solvent extraction feed solution. Finally, as a result of component analysis of the solvent extraction feed solution obtained by adjusting the pH of the leaching solution, Cu, It was confirmed that Fe and Al were completely removed (Table 1).
실시예Example 2: 2: 폐리튬이온전지로부터From waste lithium ion battery CoCo 와 Wow MnMn 의 용매추출Solvent extraction
실시예 1의 폐리튬이온전지 분말의 침출액으로부터 얻어진 용매추출 Feed용액에 대해, Cyanex 272 용매를 이용하여, 비누화도 및 세척횟수를 포함하는 최적의 Co와 Mn 선택적 추출 조건을 선별하고자 다음의 실험을 수행하였다.For the solvent extraction feed solution obtained from the leachate of the waste lithium ion battery powder of Example 1, the following experiment was performed to select the optimal Co and Mn selective extraction conditions including the degree of saponification and the number of washes using a Cyanex 272 solvent. Was performed.
2-1. 0.7M 2-1. 0.7M CyanexCyanex 272의 40% 및 50% 272 40% and 50% 비누화된Saponified 용매를 이용한 Solvent CoCo 및 And MnMn 추출 extraction
실시예 1에서 얻어진 폐리튬이온전지 유래 용매추출 Feed용액에 대해, NaOH를 사용하여 40% 및 50%로 비누화된 0.7 M bis(2,4,4-trimethyl pentyl) phosphinic acid(Cyanex 272, Cytec Inc., USA)를 유기상(organic phase)에 대해 0/A(Organic/Aqueous) = 2:1 (40ml:20ml)의 함량으로 혼합하여 5 min 동안 25℃에서 교반하면서 1회 추출을 시행하였다.For the solvent extraction feed solution derived from the waste lithium ion battery obtained in Example 1, 0.7 M bis (2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272, Cytec Inc., saponified to 40% and 50% using NaOH). , USA) was mixed with an organic phase of 0 / A (Organic / Aqueous) = 2: 1 (40 ml: 20 ml) and subjected to one extraction with stirring at 25 ° C. for 5 min.
그 결과, [표 2]의 초기 용매추출 feed 용액의 성분에 대해, 서로 다른 비누화도에 따라서, [표 3]에 나타난 바와 같이, Raffinate로 Co, Ni, Li, Mn, Cu 성분이 추출되어 나왔으며, 결과적으로 0.7M Cyanex 272의 비누화도에 따른 Co와 Mn의 추출율은 40% 비누화 조건에서는 각각 68.7%, 93.2%였으며, 50% 비누화 조건에서는 80.7%, 94.5%인 것으로 나타났다(표 4). 이외에 불순물인 Cu와 Al의 경우 매우 높은 추출율을 보였으나 용액 내 함량이 1-2 ppm 정도이기 때문에 크게 의미는 없다.As a result, for the components of the initial solvent extraction feed solution of [Table 2], according to the degree of saponification, Co, Ni, Li, Mn, Cu components were extracted with Raffinate as shown in [Table 3]. As a result, the extraction rates of Co and Mn according to saponification degree of 0.7M Cyanex 272 were 68.7% and 93.2% under 40% saponification conditions, and 80.7% and 94.5% under 50% saponification conditions (Table 4). In addition to the impurities Cu and Al showed a very high extraction rate, but because the content in the solution is about 1-2 ppm is not significant.
상기 과정으로 추출된 용매에 대해, 추가로 세척과정을 거침으로써, 추출율이 어느 정도 향상되는지를 관찰하였다. 상기 추출된 용매의 세척조건은 O/A=2:1 (40ml:20ml)의 조건에서 60℃의 증류수를 이용하여 1분 동안 교반 하였으며 3회 반복실시하였다.With respect to the solvent extracted in the above process, by further washing, it was observed how much the extraction rate is improved. Washing conditions of the extracted solvent was stirred for 1 minute using distilled water at 60 ℃ under conditions of O / A = 2: 1 (40ml: 20ml) and repeated three times.
그 결과, 40% 및 50% 비누화된 용매를 이용한 추출용매 모두에 대해 3회세척을 통하여 잔여 Ni, Li의 완전히 제거됨을 확인하였다(표 5 및 6).As a result, it was confirmed that residual Ni and Li were completely removed through three washes for both the extraction solvent using 40% and 50% saponified solvent (Tables 5 and 6).
2-2. 2-2. HBrHBr 용액을 이용한 Solution 탈거용액의Stripping solution 제조 Produce
실시예 2-1에서 비누화된 0.7M Cyanex 272에 의해 추출된 추출용매에 대하여, 2M HBr 용액을 O/A=4:1의 혼합비를 갖도록 한 후, 5분동안 교반하면서 1 회 탈거하였다. 그 결과, 40% 비누화 조건에서 얻어진 추출용매로부터의 Co와 Mn의 탈거효율은 각각 79.3% 및 85.3% 였고 50% 비누화 조건에서 얻어진 추출용매의 Co와 Mn의 탈거효율은 85.2% 및 79.4%인 것으로 확인되었다(표 7 및 8).To the extraction solvent extracted with 0.7M Cyanex 272 saponified in Example 2-1, 2M HBr solution was allowed to have a mixing ratio of O / A = 4: 1, and then stripped once with stirring for 5 minutes. As a result, the removal efficiencies of Co and Mn from the extraction solvents obtained at 40% saponification conditions were 79.3% and 85.3%, respectively. The removal efficiencies of Co and Mn of extraction solvents obtained at 50% saponification conditions were 85.2% and 79.4%. It was confirmed (Tables 7 and 8).
실시예Example 3: 폐 3: lung 3원계Ternary 양극활물질Cathode active material 침출액으로부터 From leachate CoCo 와 Wow MnMn 의 용매추출Solvent extraction
실시예 1의 폐 3원계 양극활물질 침출액으로부터 얻어진 용매추출 Feed용액에 대해, Cyanex 272 용매를 이용하여, 비누화도 및 세척횟수를 포함하는 최적의 Co와 Mn 선택적 추출조건을 선별하고자 다음의 실험을 수행하였다.For the solvent extraction feed solution obtained from the waste ternary cathode active material leaching solution of Example 1, the following experiment was performed to select the optimal Co and Mn selective extraction conditions including the degree of saponification and the number of washings using a Cyanex 272 solvent. It was.
3-1. 0.85M 3-1. 0.85M CyanexCyanex 272의 40%, 45% 및 50% 272 40%, 45% and 50% 비누화된Saponified 용매를 이용한 Solvent CoCo 및 And MnMn 추출 extraction
실시예 1에서 얻어진 폐 3원계 양극활물질 침출액 유래 용매추출 Feed용액에 대해, NaOH를 사용하여 40%, 45% 및 50%로 비누화된 0.85 M bis(2,4,4-trimethyl pentyl) phosphinic acid(Cyanex 272, Cytec Inc., USA)를 유기상(organic phase)에 대해 0/A(Organic/Aqueous) = 2:1 (40ml:20ml)의 비율로 혼합하여 5 min 동안 25℃에서 교반하면서 1회 추출을 시행하였다.For the solvent extraction feed solution derived from the waste ternary positive electrode active material leaching solution obtained in Example 1, 0.85 M bis (2,4,4-trimethyl pentyl) phosphinic acid saponified to 40%, 45% and 50% using NaOH. Cyanex 272, Cytec Inc., USA) was mixed with organic phase at a ratio of 0 / A (Organic / Aqueous) = 2: 1 (40ml: 20ml) and extracted once with stirring at 25 ° C for 5 min. Was implemented.
그 결과, [표 9]의 초기 용매추출 feed 용액의 성분에 대해, 서로 다른 비누화도에 따라서, [표 10]에 나타난 바와 같이, Raffinate로 Co, Ni, Li, Mn, Cu 성분이 추출되어 나왔으며, 결과적으로 0.85M Cyanex 272의 비누화도에 따른 Co와 Mn의 추출율은 40% 비누화 조건에서는 56.7%, 78.8%, 45% 비누화조건에서는 62.1%, 84.6%, 및 50% 비누화 조건에서는 77.4%, 94.6%로 나타났으며, Co와 Mn의 추출율은 비누화도가 증가함에 따라 추출율도 같이 증가하는 것으로 확인하였다. 그러나 불순물인 Li의 경우에는 40% 비누화 조건에서 4%, 45% 비누화조건에서는 3.5%, 그리고 50% 비누화 조건에서 11.7%가 함께 추출되는 것으로 나타났다(표 11).As a result, Co, Ni, Li, Mn, Cu components were extracted with Raffinate as shown in [Table 10] for the components of the initial solvent extraction feed solution of [Table 9] according to different degree of saponification. As a result, the extraction rates of Co and Mn according to the saponification degree of 0.85M Cyanex 272 were 56.7%, 78.8% at 40% saponification condition, 62.1% at 8% saponification condition, 84.6%, and 77.4% at 50% saponification condition. The extraction rate of Co and Mn was found to increase with the increase of saponification. However, in the case of Li as an impurity, 4% at 40% saponification condition, 3.5% at 45% saponification condition, and 11.7% at 50% saponification condition were extracted together (Table 11).
상기 과정으로 추출된 용매에 대해, 추가로 세척과정을 거침으로써, 추출율이 어느정도 향상되는 지를 관찰하였다. 상기 추출된 용매의 세척조건은 O/A=2:1 (40ml:20ml)의 조건에서 60℃의 증류수를 이용하여 1분 간 교반하였으며, 3회 반복실시하였다.For the solvent extracted by the above process, by further washing, it was observed how much the extraction rate is improved. Washing conditions of the extracted solvent was stirred for 1 minute using distilled water at 60 ℃ under conditions of O / A = 2: 1 (40ml: 20ml), it was repeated three times.
그 결과, 40% 비누화된 용매를 이용한 추출용매에 대해 3회세척을 통해 잔여 Ni, Li의 비교적 완벽하게 제거됨을 확인하였으며, 45% 및 50% 비누화된 용매를 이용한 추출용매에서도 3회세척을 통해 불순물이 제거됨을 확인하였다(표 12, 13 및 14).As a result, it was confirmed that the residual Ni and Li were relatively completely removed by three washings with the extraction solvent using 40% saponified solvent, and three times with the extraction solvent using 45% and 50% saponified solvent It was confirmed that impurities were removed (Tables 12, 13 and 14).
3-2. 3-2. HBrHBr 용액을 이용한 Solution 탈거용액의Stripping solution 제조 Produce
실시예 3-1에서 비누화된 0.85M Cyanex 272에 의해 추출된 추출용매에 대하여, 2M HBr 용액을 O/A=4:1의 혼합비를 갖도록 한 후, 5분 동안 교반하면서 1 회 탈거하였다. 그 결과, 40% 비누화 조건에서 Co와 Mn의 탈거효율은 각각 97% 및 84.4%인 것으로 나타났으며, 45% 비누화 조건에서는 86.9% 및 100.7%, 그리고 50% 비누화 조건에서의 탈거반응에서는 1단 탈거에서는 완전한 탈거가 이루어지지 않아, 2단 탈거를 진행하여 탈거액을 얻었고, 2단 탈거의 Co와 Mn의 탈거 효율은 100% 및 92.2% 인 것으로 확인되었다(표 15 및 16).For the extraction solvent extracted with 0.85M Cyanex 272 saponified in Example 3-1, 2M HBr solution was allowed to have a mixing ratio of O / A = 4: 1, and then stripped once with stirring for 5 minutes. As a result, the stripping efficiency of Co and Mn at 40% saponification condition was 97% and 84.4%, respectively, 86.9% and 100.7% at 45% saponification condition, and one stage at stripping reaction at 50% saponification condition. In the stripping, complete stripping was not carried out, and stripping liquid was obtained by performing two-stage stripping, and the stripping efficiency of Co and Mn in two-stage stripping was confirmed to be 100% and 92.2% (Tables 15 and 16).
실시예Example 3. 3. 탈거용액으로부터From stripping solution CMBCMB 액상 촉매의 제조 Preparation of Liquid Catalyst
실시예 2-2 및 3-2에서 제조된 탈거용액(Co-Mn-Br 탈거용액)으로부터 CMB 액상촉매를 제조하기 위하여, CMB 액상촉매의 성분(CMB spec.) 및 제조된 탈거용액의 성분을 이온크로마토그래피 및 ICP를 이용하여 측정하였다(표 17).To prepare a CMB liquid catalyst from the stripping solution (Co-Mn-Br stripping solution) prepared in Examples 2-2 and 3-2, the components of the CMB liquid catalyst (CMB spec.) And the stripping solution of the prepared stripping solution were prepared. It was measured using ion chromatography and ICP (Table 17).
그 결과, CMB 액상촉매를 구성하는데는 탈거용액에 함유된 각각의 성분이 부족하기 때문에, CMB 액상촉매의 중간산물인 탈거용액으로부터 CMB 액상촉매를 제조하기 위하여 cobalt bromide및 manganese bromide 그리고 manganese acetate를 추가하여 제조하였다. CMB 액상촉매를 제조하는데 필요한 첨가량은 추출조건에 따라 다르며, 성분 분석에 따라 Co-Mn-Br의 농도를 CMB spec.과 동일하도록 [표 18]의 농도로 첨가하여 CMB 액상촉매를 제조하였다.As a result, the cobalt bromide, manganese bromide and manganese acetate were added to prepare the CMB liquid catalyst from the stripping solution, which is an intermediate product of the CMB liquid catalyst, because each component contained in the stripping solution was insufficient in forming the CMB liquid catalyst. It was prepared by. The amount required to prepare the CMB liquid catalyst is different depending on the extraction conditions, and according to the component analysis was added to the concentration of Co-Mn-Br in the concentration of [Table 18] to the same as the CMB spec.
실험예Experimental Example 1: 용매의 1: solvent 비누화도에On saponification 따른 According CoCo 및 And MnMn 추출효율 시뮬레이션 테스트 Extraction Efficiency Simulation Test
1-1. 폐리튬이온전지로부터 Co 및 Mn 추출효율 시뮬레이션 1 -1. From waste lithium ion battery Co and Mn Extraction Efficiency Simulation
실시예 1의 폐리튬이온전지 분말의 침출액으로부터 얻어진 용매추출 Feed용액에 대해, 0.7M Cyanex 272(Cytec Inc., USA) 용매의 비누화도에 따른 Co와 Mn 추출 효율 시뮬레이션 테스트를 실시하였다. 모든 용매추출 및 탈거과정은 O/A=2:1 (40ml:20ml), 25℃에서 교반시간 5 분의 조건으로 수행하였다.For the solvent extraction feed solution obtained from the leachate of the waste lithium ion battery powder of Example 1, Co and Mn extraction efficiency simulation tests were performed according to the saponification degree of the 0.7 M Cyanex 272 (Cytec Inc., USA) solvent. All solvent extraction and stripping process was carried out under O / A = 2: 1 (40ml: 20ml), a stirring time of 5 minutes at 25 ℃.
0.7M cyanex 272의 40% 비누화된 용매를 이용하여 2 step count-current extraction simulation 추출하여본 결과, Co의 추출율은 99.6%, Mn은 93.3%가 추출된 것으로 확인되었다. 또한, 1단 추출의 경우에 Co는 6.9%, Mn은 79.9% 였으며 Li과 Ni의 경우에는 모두 (-) 추출율을 보이는 것을 보아 전혀 추출이 되지 않음을 확인할 수 있었다. 최종적으로 raffinate로 빠져나가는 Co와 Mn의 양은 각각 89.3 mg/L, 0.542 mg/L인 것으로 나타났다(표 19 및 20, 도 2)As a result of 2 step count-current extraction simulation extraction using 40% saponified solvent of 0.7M cyanex 272, Co extraction rate was 99.6% and Mn was 93.3%. In the case of one-stage extraction, Co was 6.9%, Mn was 79.9%, and both Li and Ni showed negative extraction ratios. Finally, the amounts of Co and Mn exiting raffinate were 89.3 mg / L and 0.542 mg / L, respectively (Tables 19 and 20, Fig. 2).
1-2. 폐 3원계 양극활물질 침출액으로부터 Co 및 Mn 추출효율 시뮬레이션 1 -2. Lung ternary system Simulation of Co and Mn Extraction Efficiency from Cathode Active Material Leachate
실시예 1의 폐 3원계 양극활물질 침출액으로부터 얻어진 용매추출 Feed용액에 대해, 0.85M Cyanex 272(Cytec Inc., USA) 용매의 비누화도에 따른 Co와 Mn 추출 효율 시뮬레이션 테스트를 실시하였다. 모든 용매추출 및 탈거과정은 O/A=2:1 (40ml:20ml), 25℃에서 교반시간 5 분의 조건으로 수행하였다.The solvent extraction feed solution obtained from the waste ternary positive electrode active material leaching solution of Example 1 was subjected to a simulation test of Co and Mn extraction efficiency according to the saponification degree of the solvent of 0.85M Cyanex 272 (Cytec Inc., USA). All solvent extraction and stripping process was carried out under O / A = 2: 1 (40ml: 20ml), a stirring time of 5 minutes at 25 ℃.
0.85M cyanex 272의 45% 비누화된 용매를 이용하여 2 step count-current extraction simulation 추출하여본 결과, Co의 추출율은 99.8% 였고 Mn은 100% 추출되었다. 1단 추출의 경우에 Co는 -14.1%, Mn은 55.2% 였으며 불순물인 Ni의 경우에는 (-) 추출율을 보이는 것을 보아 전혀 추출이 되지 않음을 확인할 수 있었으나 Li의 경우 0.3% 추출되는 것을 확인할 수 있었다. 최종 Raffinate로 빠져나가는 Co와 Mn의 양은 각각 17.48 mg/L, 1.179 mg/L였고 추출되는 Li의 총량은 18 mg/L인 것으로 확인되었다(표 21 및 22, 도 3)Two-step count-current extraction simulation extraction using 45% saponified solvent of 0.85M cyanex 272 showed that the Co extraction rate was 99.8% and Mn was 100% extracted. In the case of one-stage extraction, Co was -14.1%, Mn was 55.2%, and in case of impurity Ni, it was confirmed that the extraction was not performed at all. there was. The amounts of Co and Mn exiting the final Raffinate were 17.48 mg / L and 1.179 mg / L, respectively, and the total amount of Li extracted was found to be 18 mg / L (Tables 21 and 22, FIG. 3).
결론적으로, 폐리튬이온전지 침출액의 pH 조절액의 경우에는 0.7M Cyanex 272 40% 비누화된 조건에서 Co와 Mn의 선택적인 추출이 가능하였고, 추출율 역시 Co는 99.6%, Mn은 93.3%로 매우 높음을 확인할 수 있었다. 또한 폐 3원계 양극활물질 침출액의 0.85M Cyanex 272 45% 비누화된 조건에서 Co와 Mn을 추출하여야 하며 이때 추출율은 각각 99.8%, 100% 였다.In conclusion, in the case of the pH control solution of the lithium ion battery leachate, it was possible to selectively extract Co and Mn under 0.7M Cyanex 272 40% saponified condition, and the extraction rate was 99.6% for Co and 93.3% for Mn. Could confirm. In addition, Co and Mn were extracted under 0.85M Cyanex 272 45% saponified condition of the waste ternary cathode active material leachate. The extraction rates were 99.8% and 100%, respectively.
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.
도 1은 Co-Mn-Br계 액상촉매의 제조를 위한 공정도이다.1 is a process chart for the preparation of Co-Mn-Br-based liquid catalyst.
도 2는 0.7M Cyanex 272의 40% 비누화 용매를 이용한 주요 원소의 회수 시뮬레이션 테스트 모식도이다.FIG. 2 is a schematic diagram of a recovery simulation test of major elements using 40% saponification solvent of 0.7M Cyanex 272. FIG.
도 3은 0.85M Cyanex 272의 45% 비누화 용매를 이용한 주요 원소의 회수 시뮬레이션 테스트 모식도이다.3 is a schematic diagram of the recovery simulation test of the main elements using 45% saponification solvent of 0.85M Cyanex 272.
Claims (10)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20090116570A KR101089519B1 (en) | 2009-11-30 | 2009-11-30 | Method for Producing CMB Catalyst recycled with Lithium Ion Battery and Ternary Cathode Materials |
JP2012541932A JP5572222B2 (en) | 2009-11-30 | 2010-11-04 | Method for producing CMB liquid phase catalyst from lithium ion battery and ternary positive electrode active material |
CN2010800535942A CN102665912A (en) | 2009-11-30 | 2010-11-04 | Method for producing CMB catalyst recycled with lithium ion battery and ternary cathode materials |
PCT/KR2010/007750 WO2011065682A2 (en) | 2009-11-30 | 2010-11-04 | Method for producing cmb catalyst recycled with lithium ion battery and ternary cathode materials |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20090116570A KR101089519B1 (en) | 2009-11-30 | 2009-11-30 | Method for Producing CMB Catalyst recycled with Lithium Ion Battery and Ternary Cathode Materials |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1020110093481A Division KR101109031B1 (en) | 2011-09-16 | 2011-09-16 | Method for Producing CMB Catalyst recycled with Lithium Ion Battery and Ternary Cathode Materials |
Publications (2)
Publication Number | Publication Date |
---|---|
KR20110060089A KR20110060089A (en) | 2011-06-08 |
KR101089519B1 true KR101089519B1 (en) | 2011-12-05 |
Family
ID=44067045
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR20090116570A KR101089519B1 (en) | 2009-11-30 | 2009-11-30 | Method for Producing CMB Catalyst recycled with Lithium Ion Battery and Ternary Cathode Materials |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP5572222B2 (en) |
KR (1) | KR101089519B1 (en) |
CN (1) | CN102665912A (en) |
WO (1) | WO2011065682A2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108011144A (en) * | 2017-10-31 | 2018-05-08 | 合肥国轩高科动力能源有限公司 | A kind of recovery processing technique of ternary cathode material of lithium ion battery |
KR102154599B1 (en) * | 2019-04-30 | 2020-09-10 | 코스모에코켐(주) | Method for Separation and Recovery of Valuable Metals from Cathode Active Material |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101189798B1 (en) * | 2011-08-17 | 2012-10-10 | 한국지질자원연구원 | Method for producing cobalt-manganese-acetic acid(cma) catalyst from spent cobalt-manganese-bromine (cmb) catalyst |
JP5406260B2 (en) * | 2011-09-29 | 2014-02-05 | Jx日鉱日石金属株式会社 | Method for separating aluminum and manganese |
JP5847742B2 (en) * | 2013-02-18 | 2016-01-27 | Jx日鉱日石金属株式会社 | Waste cathode material and method for recovering metal from waste battery |
JP5847741B2 (en) * | 2013-02-18 | 2016-01-27 | Jx日鉱日石金属株式会社 | Waste cathode material and method for recovering metal from waste battery |
JP5706457B2 (en) * | 2013-02-27 | 2015-04-22 | Jx日鉱日石金属株式会社 | Method for separating and recovering metal from mixed metal solution |
JP6290633B2 (en) * | 2014-01-22 | 2018-03-07 | Jx金属株式会社 | Lithium ion battery waste treatment method and metal recovery method using the same |
EP3202928B1 (en) * | 2014-09-30 | 2023-11-01 | JX Nippon Mining & Metals Corporation | Leaching method for lithium ion battery scrap and method for recovering metal from lithium ion battery scrap |
KR101919724B1 (en) * | 2014-09-30 | 2018-11-16 | 제이엑스금속주식회사 | Leaching method for lithium ion battery scrap and method for recovering metal from lithium ion battery scrap |
KR101528507B1 (en) | 2015-01-13 | 2015-06-12 | 한국지질자원연구원 | Co-recovery method of cobalt and manganese from litium cells |
US10807879B2 (en) | 2016-03-16 | 2020-10-20 | Jx Nippon Mining & Metals Corporation | Processing method for lithium ion battery scrap |
US10865462B2 (en) | 2016-03-16 | 2020-12-15 | Jx Nippon Mining & Metals Corporation | Processing method for lithium ion battery scrap |
KR20200096965A (en) * | 2017-12-19 | 2020-08-14 | 바스프 에스이 | Battery recycling by treatment of leachate using metallic nickel |
KR102206952B1 (en) * | 2019-04-22 | 2021-01-25 | 코스모에코켐(주) | Manufacturing Method of Mixed Metal Compounds for Preparing Precursors from Waste Cathode Active Material Powders |
JP7365846B2 (en) * | 2019-10-16 | 2023-10-20 | Jx金属株式会社 | Method for producing high purity cobalt sulfate solution and method for producing cobalt sulfate |
CN113802002B (en) * | 2021-08-17 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for recovering valuable metals in lithium battery by wet process |
CN113846219B (en) * | 2021-09-06 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for extracting lithium from waste lithium batteries |
CN116103499A (en) * | 2023-02-16 | 2023-05-12 | 西安金藏膜环保科技有限公司 | Method for leaching valuable metals from waste lithium batteries by photoelectrocatalysis of double photoelectrodes |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003203680A (en) | 2002-01-08 | 2003-07-18 | Sumitomo Metal Mining Co Ltd | Method of recovering valuable metal from used nickel- hydrogen secondary cell |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0448038A (en) * | 1990-06-15 | 1992-02-18 | Daihachi Chem Ind Co Ltd | Method for separating indium and method for separating indium and gallium |
DE4445496A1 (en) * | 1994-12-20 | 1996-06-27 | Varta Batterie | Process for the recovery of metals from used nickel-metal hydride accumulators |
US5759229A (en) * | 1996-07-29 | 1998-06-02 | Feitler; David | Method for recovering cobalt/manganese/bromine values from residue containing used catalyst |
JPH10287864A (en) * | 1997-04-14 | 1998-10-27 | Nippon Chem Ind Co Ltd | Recovery of valuable metal from active material of positive electrode for lithium ion secondary battery |
TWI231063B (en) * | 2003-11-14 | 2005-04-11 | Ind Tech Res Inst | Process of recovering valuable metals from waste secondary batteries |
JP4388091B2 (en) * | 2007-03-22 | 2009-12-24 | 日鉱金属株式会社 | Noble metal recovery method from Co, Ni, Mn containing battery |
JP4865745B2 (en) * | 2008-02-13 | 2012-02-01 | Jx日鉱日石金属株式会社 | Method for recovering valuable metals from lithium batteries containing Co, Ni, Mn |
CN101586192B (en) * | 2009-06-23 | 2011-03-16 | 四川师范大学 | Leaching method for anode and cathode mixed materials of waste LiCoxNiyMnzO2 battery |
-
2009
- 2009-11-30 KR KR20090116570A patent/KR101089519B1/en active IP Right Grant
-
2010
- 2010-11-04 WO PCT/KR2010/007750 patent/WO2011065682A2/en active Application Filing
- 2010-11-04 JP JP2012541932A patent/JP5572222B2/en active Active
- 2010-11-04 CN CN2010800535942A patent/CN102665912A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003203680A (en) | 2002-01-08 | 2003-07-18 | Sumitomo Metal Mining Co Ltd | Method of recovering valuable metal from used nickel- hydrogen secondary cell |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108011144A (en) * | 2017-10-31 | 2018-05-08 | 合肥国轩高科动力能源有限公司 | A kind of recovery processing technique of ternary cathode material of lithium ion battery |
KR102154599B1 (en) * | 2019-04-30 | 2020-09-10 | 코스모에코켐(주) | Method for Separation and Recovery of Valuable Metals from Cathode Active Material |
Also Published As
Publication number | Publication date |
---|---|
KR20110060089A (en) | 2011-06-08 |
WO2011065682A2 (en) | 2011-06-03 |
CN102665912A (en) | 2012-09-12 |
WO2011065682A3 (en) | 2011-10-06 |
JP2013512345A (en) | 2013-04-11 |
JP5572222B2 (en) | 2014-08-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101089519B1 (en) | Method for Producing CMB Catalyst recycled with Lithium Ion Battery and Ternary Cathode Materials | |
KR101220149B1 (en) | Method for making sulfate solution of valuable metal from used battery and for making cathode active material | |
CN108886181B (en) | Re-lithiation under oxidizing conditions | |
CN104105803B (en) | The recovery method of lithium | |
KR101708149B1 (en) | A Method For Recovering Lithium Compound From An Anode Material In Spent Lithium Batteries By Wet-Milling | |
KR101201947B1 (en) | Method for recovering valuable metals from lithium secondary battery wastes | |
KR101083351B1 (en) | Method of extracting cobalt and manganese from waste cmb catalyst and method of manufacturing cmb catalyst using the same | |
KR102132120B1 (en) | A recycling method for the spent lithium ion secondary battery using carbon dioxide | |
CN113802002B (en) | Method for recovering valuable metals in lithium battery by wet process | |
KR101178768B1 (en) | Method of recovery of lithium from cathodic active material of lithium battery | |
KR20110117024A (en) | Method for reusing valuable metal of used battery | |
KR20210075502A (en) | Method for recovering valuable metals from cathodic active material of used lithium battery | |
KR102442036B1 (en) | Method for recovery of manganese compounds from cathode active material of waste lithium ion battery | |
KR101066166B1 (en) | Method for Recovering Cobalt from Waste Lithium Ion Battery | |
KR20210156539A (en) | Method of recycling active metal of lithium secondary battery utilizing the same | |
KR101109031B1 (en) | Method for Producing CMB Catalyst recycled with Lithium Ion Battery and Ternary Cathode Materials | |
KR101802071B1 (en) | A Method For Recovering Lithium Compound From An Anode Material In Spent Lithium Batteries By Wet-Milling | |
JP6314730B2 (en) | Method for recovering valuable metals from waste nickel metal hydride batteries | |
KR101351523B1 (en) | Method of recovering cadmiun from mixed spent batteries | |
KR101372622B1 (en) | Method for preparing nmc(ni-co-mn) hydroxide from ni ore | |
Junior et al. | Promising technologies under development for recycling, remanufacturing, and reusing batteries: an introduction | |
KR20130048811A (en) | Method for making cathode active material from used battery | |
KR20220057136A (en) | Method for recovering mixed solution for prepararing precursor from ternary cathode active material of spent lithium ion batteries | |
KR20220134387A (en) | Method for recovering valuable metals from spent cathodic active material | |
KR102295564B1 (en) | Rare metal recovery method from waste lithium secondary battery |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
E902 | Notification of reason for refusal | ||
A107 | Divisional application of patent | ||
E701 | Decision to grant or registration of patent right | ||
GRNT | Written decision to grant | ||
FPAY | Annual fee payment |
Payment date: 20140925 Year of fee payment: 4 |
|
FPAY | Annual fee payment |
Payment date: 20151001 Year of fee payment: 5 |
|
FPAY | Annual fee payment |
Payment date: 20161004 Year of fee payment: 6 |
|
FPAY | Annual fee payment |
Payment date: 20170918 Year of fee payment: 7 |
|
FPAY | Annual fee payment |
Payment date: 20180927 Year of fee payment: 8 |
|
FPAY | Annual fee payment |
Payment date: 20191001 Year of fee payment: 9 |