KR20240087025A - Manufacturing method of lithium carbonate using spodumene - Google Patents
Manufacturing method of lithium carbonate using spodumene Download PDFInfo
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- spodumene
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- lithium
- lithium carbonate
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 45
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052642 spodumene Inorganic materials 0.000 title claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002386 leaching Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 13
- 239000011707 mineral Substances 0.000 claims abstract description 13
- 239000012153 distilled water Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 150000002642 lithium compounds Chemical class 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000011085 pressure filtration Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 16
- 239000000243 solution Substances 0.000 description 12
- 235000010755 mineral Nutrition 0.000 description 11
- 239000012535 impurity Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 8
- 239000012267 brine Substances 0.000 description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000000378 calcium silicate Substances 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910018091 Li 2 S Inorganic materials 0.000 description 2
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- -1 lithium sulfate compound Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/22—Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
본 발명은 스포듀민을 이용한 탄산리튬 제조방법에 관한 것으로서, 준비된 리튬함유광물 분말인 Spodumene-α를 대기분위기에서 열처리하여 Spodumene-β으로 상변화시키는 제1 단계와, 상기 Spodumene-β 분말과, 황산용액을 2:1 내지 3:2 비율로 혼합하여 제1 혼합물을 취득하고, 취득된 상기 제1 혼합물을 열처리하여 Li2SO4으로 상변화시키는 제2 단계와, 상기 Li2SO4 분말과, 탄소분물을 1:1 내지 1:2 비율로 혼합하여 제2 혼합물을 취득하고, 취득된 상기 제2 혼합물을 열처리하여 Li2CO3 분말을 상분리하는 제3 단계와, 상분리된 상기 Li2CO3 분말을 증류수로 침출처리하여 액체상태의 Li2CO3를 회수하는 제4 단계를 포함하는 것을 특징으로 하는 스포듀민을 이용한 탄산리튬 제조방법를 제공한다.
상기와 같은 본 발명에 따르면, 제조공정을 간소화하여 작업시간을 크게 단축시켜 제조단가를 절감할 수 있고, 고순도이면서 높은 회수율을 확보할 수 있을 뿐 아니라 기존 방식 대비 친환경적인 특징이 있다.The present invention relates to a method for producing lithium carbonate using spodumene, which includes a first step of phase changing the prepared lithium-containing mineral powder, Spodumene-α, into Spodumene-β by heat treatment in an atmospheric atmosphere, the Spodumene-β powder, and sulfuric acid. A second step of mixing the solutions at a ratio of 2:1 to 3:2 to obtain a first mixture, heat treating the obtained first mixture to change the phase into Li 2 SO 4 , the Li 2 SO 4 powder, and A third step of mixing carbon powder at a ratio of 1:1 to 1:2 to obtain a second mixture, heat treating the obtained second mixture to phase separate Li 2 CO 3 powder, and the phase-separated Li 2 CO 3 powder A method for producing lithium carbonate using spodumene is provided, which includes a fourth step of recovering Li 2 CO 3 in a liquid state by leaching with distilled water.
According to the present invention as described above, the manufacturing process can be simplified and the working time can be greatly shortened to reduce the manufacturing cost, and not only can high purity and high recovery rate be secured, but it is also more environmentally friendly than the existing method.
Description
본 발명은 스포듀민을 이용한 탄산리튬 제조방법에 관한 것으로서, 보다 상세하게는 제조공정을 간소화하여 작업시간을 크게 단축시켜 제조단가를 절감할 수 있고, 고순도이면서 높은 회수율을 확보할 수 있을 뿐 아니라 기존 방식 대비 친환경적인 기술에 관한 것이다.The present invention relates to a method for manufacturing lithium carbonate using spodumene. More specifically, it simplifies the manufacturing process, greatly shortens the working time, reduces manufacturing cost, secures high purity and high recovery rate, and improves existing lithium carbonate. It is about eco-friendly technology compared to other methods.
일반적으로 탄산리튬은 황산법을 이용하거나 석회법을 이용한 방법 등 다양한 방법이 사용되고 있는데, 일예들을 살펴보면 아래와 같다.In general, various methods are used for lithium carbonate, such as using the sulfuric acid method or the lime method. Examples are as follows.
황산법을 이용한 탄산리튬 제조방법Method for producing lithium carbonate using the sulfuric acid method
리튬함유광물로부터 리튬화합물을 제조하는 방법 중 하나인 황산법은 리튬함유광물을 분쇄한 미분 분말에 이론양보다 많은 황산을 혼합한 뒤, 황산배소로에서 약 250℃로 가열하여, 황산리튬상(Li2SO4)으로 변환한다. 변환된 황산리튬상(Li2SO4)을 농축, 여과, 산 침출 공정을 통해 철, 알루미늄, 유기물 등의 불순물을 제거하여 순도를 향상시킨 뒤 소다회와 반응시켜 리튬화합물인 탄산리튬(Li2SO4)로 제조한다.The sulfuric acid method, which is one of the methods for producing lithium compounds from lithium-containing minerals, involves mixing more sulfuric acid than the theoretical amount into fine powder of pulverized lithium-containing minerals, heating it to about 250°C in a sulfuric acid roaster, and producing lithium sulfate phase (Li). Convert to 2 SO 4 ). The purity of the converted lithium sulfate phase (Li 2 SO 4 ) is improved by removing impurities such as iron, aluminum, and organic substances through concentration, filtration, and acid leaching processes, and then reacted with soda ash to produce lithium carbonate (Li 2 SO ), a lithium compound. 4 ) is manufactured.
석회법을 이용한 탄산리튬 제조방법Lithium carbonate manufacturing method using lime method
석회법은 1950년대 미국의 Albermarle사가 개발한 리튬화합물 제조공정으로서, 리튬함유광물을 수산화리튬(LiOH) 형태로 변환 및 제조하는 공정이다. 리튬함유광물을 고온에서 가열함에 있어서 CaO를 첨가제로 하여 규산화칼슘(Ca2SO4)화 산화리튬(Li2O) 형태로 분리하고, 분리된 규산화칼슘(Ca2SO4)화 산화리튬(Li2O)울 고온의 용수를 통해 규산화칼슘을 제거하여 수산화리튬(LiOH) 용액을 제조한다. 제조된 수산화리튬 용액을 농축 및 건조 공정을 통해 수산화리튬 분말을 제조하는 공정이다.The lime process is a lithium compound manufacturing process developed by Albermarle in the United States in the 1950s, and is a process for converting and manufacturing lithium-containing minerals into the form of lithium hydroxide (LiOH). When heating lithium-containing minerals at high temperatures, CaO is used as an additive to separate them into calcium silicate (Ca 2 SO 4 ) and lithium oxide (Li 2 O), and then separate calcium silicate (Ca 2 SO 4 ) into lithium oxide. (Li 2 O) A lithium hydroxide (LiOH) solution is prepared by removing calcium silicate through high-temperature water. This is a process of producing lithium hydroxide powder through a concentration and drying process of the prepared lithium hydroxide solution.
염수법을 이용한 탄산리튬 제조방법Method for producing lithium carbonate using the brine method
수법 리튬 함유 염수로부터 리튬을 회수 및 리튬 화합물을 제조하는 일반적인 공정이며, 미국의 회사인 Albemarl의 Silver Peak 광산에서 개발한 리튬 화합물 제조공정으로 염수의 증발 및 약품처리를 통해 불순물 제거 후 리튬 화합물을 제조하는 공정이다. 염수법은 증발지 내에서 증발 및 결정화 작용을 적용하여 Na, Ca, Mg, Cl 등의 불순물을 제거하고 증발을 통해 리튬을 농축시킨다. 이때 제조된 리튬 농축액은 6%의 리튬 함량을 가지고 있으며, 석회를 통해 잔류 불순물인 마그네슘 및 황산염을 제거하고, 소다회를 통해 칼슘을 제거 한 뒤, 가열 및 건조하여 탄산리튬(Li2CO3)을 제조한다.This is a general process for recovering lithium and producing lithium compounds from lithium-containing brine. This is a lithium compound manufacturing process developed by the Silver Peak mine of Albemarl, an American company, and produces lithium compounds after removing impurities through evaporation and chemical treatment of brine. It is a process. The brine method applies evaporation and crystallization in an evaporation pond to remove impurities such as Na, Ca, Mg, and Cl and concentrate lithium through evaporation. The lithium concentrate prepared at this time has a lithium content of 6%, and residual impurities such as magnesium and sulfate are removed through lime, calcium is removed through soda ash, and then heated and dried to produce lithium carbonate (Li 2 CO 3 ). manufacture.
미상용화 탄산리튬 제조방법Method for manufacturing uncommercialized lithium carbonate
현재 까지는 상용화 되지 않은 공정이지만, 미국, 독인, 칠레 등의 회사에서 상용화를 위한 공정이 개발 중에 있다. 리튬 함유 점토의 경우 생석회(CaCO3)와 황산칼슘(CaSO4)를 혼합하여 분쇄 및 열처리 하여 알칼리금속황화물(Li2SO4, K2SO4, Na2SO4)와 실리카겔을 제조한다. 제조된 알칼리금속황화물은 75~90℃의 물에서 용해 후 염수를 생성하고, 이렇게 생성된 염수를 건조 시켜 황산칼륨 및 황산나트륨 결정으로 회수하고, 잔류 염수와 소다회를 반응시켜 탄산리튬(Li2CO3)을 제조한다. 이렇게 제조된 탄산리튬(Li2CO3)은 여과 및 세척을 통해 순도를 향상시키고 건조하여 분말로 만든다.Although this process has not been commercialized to date, processes for commercialization are being developed by companies in the United States, Germany, and Chile. In the case of lithium-containing clay, quicklime (CaCO 3 ) and calcium sulfate (CaSO 4 ) are mixed, crushed, and heat treated to produce alkali metal sulfide (Li 2 SO 4 , K 2 SO 4 , Na 2 SO 4 ) and silica gel. The prepared alkali metal sulfide is dissolved in water at 75-90℃ to produce brine. The brine thus produced is dried and recovered as potassium sulfate and sodium sulfate crystals, and the residual brine is reacted with soda ash to produce lithium carbonate (Li 2 CO 3 ) is manufactured. The purity of lithium carbonate (Li 2 CO 3 ) prepared in this way is improved through filtration and washing, and then dried to make powder.
위 4가지의 탄산리튬 제조공정은 리튬함유광물로부터 리튬화합물을 제조 및 회수 하기위해 현재 상용화되어 실제로 적용중인 공정이거나, 개발 중인 공정이다.The above four lithium carbonate manufacturing processes are currently commercialized and actually applied, or are under development, to produce and recover lithium compounds from lithium-containing minerals.
그러나, 이들 공정들은 대부분 탄산리튬을 제조하기 위해 고농도, 대량의 산용액이 사용되고, 산 침출 및 약품처리 과정에서 발생되는 산 용매 및 기타 폐기물, 폐수 처리에 큰 비용이 소요됨과 아울러 제조공정이 매우 복잡하여 상당한 작업시간을 요하는 바 이에 따른 경제적 부담이 가중될 뿐 아니라 환경적으도 문제가 발생되고 있는 상황이다.However, most of these processes use high-concentration, large-volume acid solutions to produce lithium carbonate, and a large cost is required to treat acid solvents, other wastes, and wastewater generated during acid leaching and chemical treatment, and the manufacturing process is very complicated. This requires a considerable amount of work time, which not only increases the economic burden but also causes environmental problems.
본 발명은 상기와 같은 문제점을 해결하기 위해 안출된 것으로서, 본 발명의 목적은 제조공정을 간소화하여 작업시간을 크게 단축시켜 제조단가를 절감할 수 있고, 고순도이면서 높은 회수율을 확보할 수 있을 뿐 아니라 기존 방식 대비 친환경적인 스포듀민을 이용한 탄산리튬 제조방법을 제공함에 있다.The present invention was created to solve the above problems, and the purpose of the present invention is to simplify the manufacturing process, significantly shorten the working time, reduce manufacturing costs, and secure high purity and high recovery rate. The aim is to provide a method for manufacturing lithium carbonate using spodumene, which is more environmentally friendly than existing methods.
상기와 같은 목적을 달성하기 위한 본 발명의 일측면에 따르면, 준비된 리튬함유광물 분말인 Spodumene-α를 대기분위기에서 열처리하여 Spodumene-β으로 상변화시키는 제1 단계와, 상기 Spodumene-β 분말과, 황산용액을 2:1 내지 3:2 비율로 혼합하여 제1 혼합물을 취득하고, 취득된 상기 제1 혼합물을 열처리하여 Li2SO4으로 상변화시키는 제2 단계와, 상기 Li2SO4 분말과, 탄소분물을 1:1 내지 1:2 비율로 혼합하여 제2 혼합물을 취득하고, 취득된 상기 제2 혼합물을 열처리하여 Li2CO3 분말을 상분리하는 제3 단계와, 상분리된 상기 Li2CO3 분말을 증류수로 침출처리하여 액체상태의 Li2CO3를 회수하는 제4 단계를 포함하는 것을 특징으로 하는 스포듀민을 이용한 탄산리튬 제조방법를 제공한다.According to one aspect of the present invention for achieving the above object, a first step of phase changing the prepared lithium-containing mineral powder, Spodumene-α, into Spodumene-β by heat treatment in an atmospheric atmosphere, the Spodumene-β powder, A second step of mixing a sulfuric acid solution in a ratio of 2:1 to 3:2 to obtain a first mixture and heat-treating the obtained first mixture to change the phase into Li 2 SO 4 , the Li 2 SO 4 powder and , a third step of mixing the carbon powder at a ratio of 1:1 to 1:2 to obtain a second mixture, heat treating the obtained second mixture to phase separate the Li 2 CO 3 powder, and the phase-separated Li 2 CO 3 powder A method for producing lithium carbonate using spodumene is provided, which includes a fourth step of recovering Li 2 CO 3 in a liquid state by leaching with distilled water.
그리고, 상기 제1 단계는 900℃ 내지 1500℃에서 열처리가 이루어지는 것이 바람직하다.In addition, the first step is preferably heat treatment performed at 900°C to 1500°C.
또한, 상기 제2 단계는 Ar 또는 N 중 어느 하나 또는 이들의 혼합 본위기에서 240℃ 내지 280℃로 열처리가 이루어질 수 있다.Additionally, the second step may be heat treated at 240°C to 280°C in either Ar or N or a mixture thereof.
아울러, 제3 단계는 CO 또는 CO2 중 어느 하나의 분위기에서 780℃ 내지 820℃로 열처리가 이루어지는 것이 바람직하다.In addition, the third step is preferably heat treatment at 780°C to 820°C in either CO or CO 2 atmosphere.
그리고, 상기 제4단계에서 회수된 상기 Li2CO3 용액을 감압여과를 통해 고순도의 리튬옹액을 회수하고, 이를 가열하여 증발 및 농축시켜 리튬화합물 분말을 제조하는 제5단계를 더 포함할 수 있다.In addition, a fifth step of recovering a high-purity lithium retaining solution through reduced pressure filtration of the Li 2 CO 3 solution recovered in the fourth step, heating, evaporating, and concentrating the solution to produce lithium compound powder may be further included. .
상기와 같은 본 발명에 따르면, 제조공정을 간소화하여 작업시간을 크게 단축시켜 제조단가를 절감할 수 있고, 고순도이면서 높은 회수율을 확보할 수 있을 뿐 아니라 기존 방식 대비 친환경적인 특징이 있다.According to the present invention as described above, the manufacturing process can be simplified and the working time can be greatly shortened to reduce the manufacturing cost, and not only can high purity and high recovery rate be secured, but it is also more environmentally friendly than the existing method.
도1은 본 발명의 일실시예에 따른 스포듀민을 이용한 탄산리튬 제조방법을 순서대로 도시한 순서도.Figure 1 is a flow chart sequentially showing a method for producing lithium carbonate using spodumene according to an embodiment of the present invention.
이하에서는 첨부된 도면을 참조하여 본 발명의 바람직한 일 실시예를 상세하게 설명하기로 한다.Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the attached drawings.
도1은 본 발명의 일실시예에 따른 스포듀민을 이용한 탄산리튬 제조방법을 순서대로 도시한 순서도이다.Figure 1 is a flow chart sequentially showing a method for producing lithium carbonate using spodumene according to an embodiment of the present invention.
도1에서 보는 바와 같이 본 발명의 일실시예에 따른 스포듀민을 이용한 탄산리튬 제조방법은 제1 단계 내지 제5단계를 거쳐 이루지는데, 아래에서 각 단계별로 살펴보도록 한다.As shown in Figure 1, the method for producing lithium carbonate using spodumene according to an embodiment of the present invention is accomplished through the first to fifth steps, and each step will be examined below.
제1 단계 - Spodumene-α의 열처리Step 1 - Heat treatment of Spodumene-α
리튬함유광물인 Spodumene-α 분말로부터 황산리튬으로의 상변화를 위해 반응성이 높은 Spodumene-β 분말로의 상변화가 요구되는데, Spodumene-β상으로의 변화는 고온에서의 열처리가 필요하며, 상변화 시 요구되는 분위기는 없다. 따라서, 본 단계에서는 대기 분위기에서 900℃ 내지 1500℃로 1시간 이상 유지하여 Spodumene-β상으로 변화한다. Spodumene-β으로 상변화하기 위한 열처리 메커니즘은 다음과 같다.In order to change the phase from Spodumene-α powder, a lithium-containing mineral, to lithium sulfate, a phase change to highly reactive Spodumene-β powder is required, and the change to Spodumene-β phase requires heat treatment at high temperature. There is no atmosphere required for poetry. Therefore, in this step, it is changed to the Spodumene-β phase by maintaining it at 900°C to 1500°C for more than 1 hour in an air atmosphere. The heat treatment mechanism for phase change to Spodumene-β is as follows.
2LiAlSi2O6(s) → Li2O·Al2O3 · 4SiO2(s)2LiAlSi 2 O 6 (s) → Li 2 O·Al 2 O 3 · 4SiO 2 (s)
제2 단계 - 황산화 열처리Second stage - sulfuration heat treatment
다음, 리튬함유광물의 고온 열처리 공정을 통해 형성된 Spodumene-β에서 리튬을 선택적으로 회수 및 제조하기 위해서는 광석 내 존재하는 리튬을 황산리튬 화합물 상으로 상변화하여야한다. Next, in order to selectively recover and manufacture lithium from Spodumene-β formed through a high-temperature heat treatment process of lithium-containing minerals, the lithium present in the ore must be phase changed into a lithium sulfate compound phase.
Spodumene-β 내 리튬을 황산리튬으로 상변화 시키기 위해 Spodumene-β 분말과 황산용액을 혼합한 후 저온에서 열처리하는데, 상세하게는 Spodumene-β 분말과 황산용액을 1:0.5의 중량비로 혼합한 뒤, 아르곤가스 분위기에서 300℃, 1시간 동안 유지하며, 이에 따른 Spodumene-β의 황산 침출의 메커니즘은 다음과 같다.In order to phase change the lithium in Spodumene-β into lithium sulfate, Spodumene-β powder and sulfuric acid solution are mixed and then heat treated at low temperature. Specifically, Spodumene-β powder and sulfuric acid solution are mixed at a weight ratio of 1:0.5. It is maintained at 300°C for 1 hour in an argon gas atmosphere, and the mechanism of sulfuric acid leaching of Spodumene-β is as follows.
Li2O · Al2O3 · 4SiO2(s) + H2SO4(l) Li 2 O · Al 2 O 3 · 4SiO 2 (s) + H 2 SO 4 (l)
→ (AlSi2)O6(s) + Li2SO4(s) + Al2(SO4)3(s) + H2O(l)↑→ (AlSi 2 )O 6 (s) + Li 2 SO 4 (s) + Al 2 (SO4) 3 (s) + H 2 O(l)↑
제3 단계 - 탄산화(Carbonation) 열처리Step 3 - Carbonation heat treatment
위 단계에서 취득된 황산리튬으로부터 고순도의 탄산리튬을 추출하기 위해서는 황산리튬을 탄산리튬으로 전환해야 하며, 탄산화(Carbonation) 공정을 통해 탄산리튬 상으로 상변화할 수 있다. In order to extract high-purity lithium carbonate from the lithium sulfate obtained in the above step, lithium sulfate must be converted to lithium carbonate, which can be phase changed to lithium carbonate through a carbonation process.
이에 본 실시예에서는 황산침출 후 취득한 분말과 탄소분말을 중량비 1:1 비율로 혼합하고, CO 또는 CO2 분위기에서 900℃로 2시간동안 열처리하였다.Accordingly, in this example, the powder obtained after sulfuric acid leaching and carbon powder were mixed at a weight ratio of 1:1, and heat treated at 900°C for 2 hours in a CO or CO 2 atmosphere.
이때, 탄산화의 메커니즘은 다음과 같다.At this time, the mechanism of carbonation is as follows.
Li2SO4 + 4C → Li2S + 4CO, Li2S + CO2 → Li2CO3 + SO2 Li 2 SO 4 + 4C → Li 2 S + 4CO, Li 2 S + CO 2 → Li 2 CO 3 + SO 2
제4 단계 - 수 침출Step 4 - Water Leaching
위 제3 단계에서는 리튬함유광물 분말로부터 탄산화를 통해 탄산리튬(Li2CO3)으로의 상분리를 수행하였으며, 본 단계에서는 탄산화를 통해 얻어진 탄산리튬(Li2CO3)과 기타 불순물과의 분리를 위해 증류수를 활용한 수침출을 수행하였다.In the third step above, phase separation was performed from the lithium-containing mineral powder into lithium carbonate (Li 2 CO 3 ) through carbonation, and in this step, lithium carbonate (Li 2 CO 3 ) obtained through carbonation was separated from other impurities. For this purpose, water leaching using distilled water was performed.
수침출은 탄산리튬(Li2CO3)과 기타 불순물에 대한 용해도 차이를 통해 분리되는 원리를 이용한 것으로서, 아래 표에 탄산리튬과 불순물의 용해도 차리를 나타내었다. Water leaching uses the principle of separating lithium carbonate (Li 2 CO 3 ) and other impurities through differences in solubility, and the solubility differences between lithium carbonate and impurities are shown in the table below.
탄산리튬 및 불순물의 물에 대한 용해도Solubility of lithium carbonate and impurities in water
표에서 볼 수 있듯이 탄산리튬이 물에 녹는 것은 발열반응으로 녹는 중 온도가 증가하기 때문에 온도가 낮아질수록 용해도가 증가하였으며, 아래에 탄산리튬이 물에 녹을 때의 반응식을 나타내었다.As can be seen in the table, the dissolution of lithium carbonate in water is an exothermic reaction, and since the temperature increases during dissolution, the solubility increases as the temperature decreases. The reaction equation when lithium carbonate is dissolved in water is shown below.
Li2CO3(s) = Li2+(aq) + CO3 2-(aq) Li 2 CO 3 (s) = Li 2+ (aq) + CO 3 2- (aq)
증류수 침출은 리튬함유광물과 증류수의 비율을 1:10, 1:20, 1:30으로 수행하였으며, 반응 시간은 1hr, 3hr, 5hr으로 수행하였다. 증류수 침출 이후 감압여과를 통해 탄산리튬 용액을 회수 하였다. Distilled water leaching was performed at a ratio of 1:10, 1:20, and 1:30 between lithium-containing minerals and distilled water, and reaction times were 1 hr, 3 hr, and 5 hr. After leaching with distilled water, the lithium carbonate solution was recovered through reduced pressure filtration.
증류수 침출 결과 리튬함유광물과 증류수의 최적 비율은 1:30으로 도출되었으며, 최적 반응시간은 5hr으로 도출되었다. 아래에 침출 결과를 나타내었다. As a result of distilled water leaching, the optimal ratio of lithium-containing minerals and distilled water was determined to be 1:30, and the optimal reaction time was determined to be 5 hr. The leaching results are shown below.
증류수 비율에 따른 여과 분말 내 탄산리튬 함량Lithium carbonate content in filtered powder according to distilled water ratio
반응 시간에 따른 여과 후 분말 내 리튬 함량Lithium content in powder after filtration according to reaction time
제5 단계 - 탄산리튬 분말 제조Step 5 - Preparation of lithium carbonate powder
최종적으로 제조한 탄산리튬 용액을 저온에서 가열하여 증발 및 농축시켜 고순도의 탄산리튬 분말을 제조하였다.The finally prepared lithium carbonate solution was heated at low temperature, evaporated, and concentrated to prepare high purity lithium carbonate powder.
리튬의 회수율은 원시료와 회수 리튬 용액의 리튬 농도를 바탕으로 산출하였으며. 순도는 ICP 무기 40종 원소 분석을 통해으로 산출 하였다. 아래에 회수율과 순도에 대한 결과를 나타내었다. The recovery rate of lithium was calculated based on the lithium concentration of the raw material and recovered lithium solution. Purity was calculated through ICP analysis of 40 inorganic elements. The results for recovery rate and purity are shown below.
황산 리튬 원시료 리튬 함량Lithium sulfate raw material lithium content
회수된 탄산 리튬 분말의 리튬 함량Lithium content of recovered lithium carbonate powder
리튬 회수율 산정식을 통해 회수율을 도출하였으며, 그 결과를 아래에 나타내었다. The recovery rate was derived using the lithium recovery rate calculation formula, and the results are shown below.
회수율(%)= 1.371g/1.439g×100 = 95.27%Recovery rate (%) = 1.371g/1.439g×100 = 95.27%
리튬 순도를 산출하기 위한 ICP-MS를 통해 제조된 탄산리튬 분말 내 무기원소 40종의 함량을 분석하였다 제조된 탄산리튬 내 불순물은 Ca, K, Mg, Na, P, Si, Sr로 총 검출량은 656.5mg/L, 1%=10000mg/L이므로 제조된 탄산리튬 내 불순물 함량은 0.066%, 순도는 99.93%로 도출되었다.The content of 40 types of inorganic elements in the manufactured lithium carbonate powder was analyzed through ICP-MS to calculate lithium purity. The impurities in the manufactured lithium carbonate were Ca, K, Mg, Na, P, Si, and Sr, and the total detected amount was Since 656.5mg/L, 1%=10000mg/L, the impurity content in the manufactured lithium carbonate was determined to be 0.066% and the purity was 99.93%.
비록 본 발명이 상기 언급된 바람직한 실시예와 관련하여 설명되어졌지만, 발명의 요지와 범위로부터 벗어남이 없이 다양한 수정이나 변형을 하는 것이 가능하다. 따라서 첨부된 특허청구의 범위는 본 발명의 요지에서 속하는 이러한 수정이나 변형을 포함할 것이다.Although the present invention has been described in connection with the above-mentioned preferred embodiments, various modifications and variations can be made without departing from the spirit and scope of the invention. Accordingly, the scope of the appended claims will include such modifications or variations as fall within the gist of the present invention.
Claims (5)
상기 Spodumene-β 분말과, 황산용액을 2:1 내지 3:2 비율로 혼합하여 제1 혼합물을 취득하고, 취득된 상기 제1 혼합물을 열처리하여 Li2SO4으로 상변화시키는 제2 단계와;
상기 Li2SO4 분말과, 탄소분물을 1:1 내지 1:2 비율로 혼합하여 제2 혼합물을 취득하고, 취득된 상기 제2 혼합물을 열처리하여 Li2CO3 분말을 상분리하는 제3 단계와;
상분리된 상기 Li2CO3 분말을 증류수로 침출처리하여 액체상태의 Li2CO3를 회수하는 제4 단계를 포함하는 것을 특징으로 하는 스포듀민을 이용한 탄산리튬 제조방법.
A first step of phase changing the prepared lithium-containing mineral powder, Spodumene-α, into Spodumene-β by heat treatment in an atmospheric atmosphere;
A second step of mixing the Spodumene-β powder and the sulfuric acid solution in a ratio of 2:1 to 3:2 to obtain a first mixture, and heat-treating the obtained first mixture to change the phase into Li 2 SO 4 ;
A third step of mixing the Li 2 SO 4 powder and carbon powder at a ratio of 1:1 to 1:2 to obtain a second mixture, and heat-treating the obtained second mixture to phase separate the Li 2 CO 3 powder; ;
The phase-separated Li 2 CO 3 powder A method for producing lithium carbonate using spodumene, comprising a fourth step of recovering liquid Li 2 CO 3 by leaching with distilled water.
상기 제1 단계는 900℃ 내지 1500℃에서 열처리가 이루어지는 것을 특징으로 하는 스포듀민을 이용한 탄산리튬 제조방법.
According to paragraph 1,
The first step is a method of producing lithium carbonate using spodumene, characterized in that heat treatment is performed at 900°C to 1500°C.
상기 제2 단계는 Ar 또는 N 중 어느 하나 또는 이들의 혼합 본위기에서 240℃ 내지 280℃로 열처리가 이루어지는 것을 특징으로 하는 스포듀민을 이용한 탄산리튬 제조방법.
According to paragraph 1,
The second step is a method of producing lithium carbonate using spodumene, characterized in that heat treatment is performed at 240°C to 280°C in either Ar or N or a mixture thereof.
제3 단계는 CO 또는 CO2 중 어느 하나의 분위기에서 780℃ 내지 820℃로 열처리가 이루어지는 것을 특징으로 하는 스포듀민을 이용한 탄산리튬 제조방법.
According to paragraph 1,
The third step is a method of producing lithium carbonate using spodumene, characterized in that heat treatment is performed at 780 ° C to 820 ° C in either CO or CO 2 atmosphere.
상기 제4단계에서 회수된 상기 Li2CO3 용액을 감압여과를 통해 고순도의 리튬옹액을 회수하고, 이를 가열하여 증발 및 농축시켜 리튬화합물 분말을 제조하는 제5단계를 더 포함하는 것을 특징으로 하는 스포듀민을 이용한 탄산리튬 제조방법.According to paragraph 1,
A fifth step of recovering a high-purity lithium retaining solution through reduced-pressure filtration of the Li 2 CO 3 solution recovered in the fourth step, heating, evaporating, and concentrating the solution to produce lithium compound powder. Method for producing lithium carbonate using spodumene.
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