KR20160064104A - Method for treating fluorine-containing liquid electrolyte - Google Patents
Method for treating fluorine-containing liquid electrolyte Download PDFInfo
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- KR20160064104A KR20160064104A KR1020167007778A KR20167007778A KR20160064104A KR 20160064104 A KR20160064104 A KR 20160064104A KR 1020167007778 A KR1020167007778 A KR 1020167007778A KR 20167007778 A KR20167007778 A KR 20167007778A KR 20160064104 A KR20160064104 A KR 20160064104A
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- electrolytic solution
- fluorine
- vaporized
- battery
- waste battery
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- 238000000034 method Methods 0.000 title claims abstract description 52
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000011737 fluorine Substances 0.000 title claims abstract description 49
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 49
- 239000011244 liquid electrolyte Substances 0.000 title 1
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 85
- 230000008016 vaporization Effects 0.000 claims abstract description 36
- 238000009834 vaporization Methods 0.000 claims abstract description 34
- 239000010926 waste battery Substances 0.000 claims abstract description 34
- 239000003513 alkali Substances 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 13
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 23
- 239000011575 calcium Substances 0.000 claims description 16
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 16
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000007789 gas Substances 0.000 description 16
- 229910013870 LiPF 6 Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 9
- 150000002222 fluorine compounds Chemical class 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- -1 ester compounds Chemical class 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229940043430 calcium compound Drugs 0.000 description 2
- 150000001674 calcium compounds Chemical class 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 150000004651 carbonic acid esters Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 239000012556 adjustment buffer Substances 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- 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
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- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4242—Regeneration of electrolyte or reactants
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/206—Organic halogen compounds
- B01D2257/2066—Fluorine
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0034—Fluorinated solvents
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- 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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
본 발명의 불소 함유 전해액의 처리 방법은, 불소 함유 전해액에 함유되는 휘발 성분을 가열하여 기화시켰을 때의 기화 잔류액에 알칼리를 첨가하여 중화하는 처리 방법으로서, 상기 불소 함유 전해액이, 폐전지 중의 전해액, 폐전지를 절단 내지 파쇄한 상태의 전해액, 사용 전의 전해액, 또는 폐전지로부터 발출된 전해액이고, 상기 전해액의 기화 잔류액에 알칼리를 첨가하여 중화하는 방법이다.A method for treating a fluorine-containing electrolytic solution according to the present invention is a treatment method for neutralizing a volatile residue contained in a fluorine-containing electrolytic solution by adding an alkali to a vaporization residue when the volatile component is vaporized by heating the electrolytic solution, wherein the fluorine- An electrolytic solution in a state in which a waste battery is cut or crushed, an electrolytic solution before use, or an electrolytic solution extracted from a spent battery, and the solution is neutralized by adding alkali to the vaporization residue of the electrolytic solution.
Description
본 발명은, 리튬 이온 전지 등에 사용되고 있는 불소 함유 전해액의 안전한 처리 방법에 관한 것이다.The present invention relates to a method for safely treating a fluorine-containing electrolytic solution used in a lithium ion battery or the like.
본원은, 2013년 9월 30일에 일본에 출원된 일본 특허출원 2013-204124호에 기초하여 우선권을 주장하고, 그 내용을 여기에 원용한다.The present application claims priority based on Japanese Patent Application No. 2013-204124 filed on September 30, 2013, the contents of which are incorporated herein by reference.
전기 자동차나 전자 기기에는 고용량의 전기를 공급하기 위해서 대형의 리튬 이온 전지가 많이 사용되고 있어, 전기 자동차나 전자 기기의 보급에 의해 대량으로 발생하는 사용 완료된 대형 전지의 처리가 문제가 되고 있다.BACKGROUND ART [0002] Large-sized lithium ion batteries are widely used in electric vehicles and electronic devices in order to supply a large amount of electricity. Thus, a large amount of used large-sized batteries generated by the spread of electric vehicles and electronic apparatuses becomes a problem.
리튬 이온 전지 등에 사용되고 있는 전해액에는, 전해질이 되는 불소 화합물 (LiPF6, LiBF4 등) 및 휘발성의 유기 용매가 함유되어 있고, 유기 용매는 주로 탄산에스테르류로서 인화성 물질이다. 또, LiPF6 은 물이나 수증기와 반응하면 가수 분해되어 유독 (有毒) 한 불화수소를 발생시킨다. 이 때문에, 안전한 처리 방법이 요구되고 있다.The electrolytic solution used in a lithium ion battery contains a fluorine compound (LiPF 6 , LiBF 4, etc.) which is an electrolyte and a volatile organic solvent, and the organic solvent is mainly a carbonic acid ester and a flammable substance. LiPF 6 , on the other hand, reacts with water or water vapor to hydrolyze and generate toxic hydrogen fluoride. For this reason, a safe processing method is required.
리튬 이온 전지나 그 전해액의 처리 방법으로서, 종래, 이하와 같은 처리 방법이 알려져 있다. (A) 리튬 이온 전지 등을 전해액의 융점 이하로 냉동시켜 전지를 해체 파쇄하고, 파쇄체를 유기 용매 중에서 전해액을 분리하여, 추출된 전해액을 증류하여 전해질과 유기 용매로 분리하는 처리 방법 (특허문헌 1), (B) 사용 완료된 리튬 전지를 배소 (焙燒) 하고, 그 배소물을 파쇄하여 자성물과 비자성물로 분별하고, 알루미늄이나 구리 등의 유용 금속량이 많은 것을 회수하는 처리 방법 (특허문헌 2), (C) 리튬 전지를 초고압수로 개구하고, 유기 용매를 사용하여 전해액을 회수하는 처리 방법 (특허문헌 3), (D) 사용 완료된 전지를 파쇄하고, 수세정 후, 정극을 박리하여 Al, Cu, Ni, Co 를 회수하고, 잔액으로부터 Li 를 용매 추출하여 회수하는 처리 방법 (특허문헌 4), (E) 사용 완료된 전지를 파쇄하고, 수세정하여 LiPF6 을 용출시키고, 정극을 박리하여 코발트산리튬을 회수하는 한편, 세정 후 액에 고온의 산을 첨가하여 LiPF6 을 인산과 불소로 분해하고, 이것에 소석회를 첨가하여, 불화 Ca 와 인산 Ca 의 혼합물을 회수하는 처리 방법 (특허문헌 5).[0003] As a method for treating a lithium ion battery or its electrolytic solution, the following treatment methods are known. (A) a treatment method in which a lithium ion battery or the like is frozen to a temperature not higher than the melting point of the electrolyte to disintegrate and break the cell, to separate the electrolyte solution in the organic solvent from the disintegration product, to distill the extracted electrolyte solution into an electrolyte and an organic solvent 1), (B) a treatment method in which a used lithium battery is roasted, the roast is crushed and separated into a magnetic product and a non-magnetic product, and a product having a large amount of useful metal such as aluminum or copper is recovered ), (C) a treatment method of opening a lithium battery with ultra-high-pressure water and recovering the electrolyte by using an organic solvent (Patent Document 3); (D) disposing a used battery, (Patent Document 4); (E) a used cell is crushed and washed to elute LiPF 6; and the positive electrode is peeled off to form cobalt mountain Processing method for recovering lithium On the other hand, after the washing was added to hot acid to the solution to decompose the LiPF 6 as phosphate and fluoride, and by the addition of slaked lime thereto, recovering a mixture of a fluoride of Ca and phosphate Ca (Patent Document 5) .
상기 처리 방법 (A) 은, 리튬 전지를 냉동 하에서 해체 파쇄하기 위해서 냉동 설비를 필요로 하므로 실시하기 어렵다. 상기 처리 방법 (B) 에서는 리튬 전지의 배소 공정에 있어서 불소가 연소 가스로서 처리되므로, 순도가 높은 불소 성분을 회수할 수 없어 불소를 재이용할 수 없다. 상기 처리 방법 (C) 에서는, 회수된 전해액의 처리가 문제가 된다. 전해액에는 인화성의 유기 용매가 함유되어 있고, 또 전해액 중의 불소 화합물은 물과 반응하여 유독한 불화수소를 발생시키므로, 안전한 처리가 요구된다. 상기 처리 방법 (D) 에서는, 유기 용매가 함유되는 세정 후 액의 처리가 문제가 된다. 상기 처리 방법 (E) 에서는, 세정 후 액에 고온의 산을 첨가하여 LiPF6 을 인산과 불소로 분해하고, 이것에 소석회를 첨가하여, 불화 Ca 와 인산 Ca 를 생성시키고 있지만, 생성되는 고형분은 불화 Ca 와 인산 Ca 의 혼합물이므로 재이용이 어렵다.The above-mentioned treatment method (A) is difficult to carry out because it requires a refrigeration facility to disassemble and disassemble the lithium battery under freezing. In the treatment method (B), since fluorine is treated as a combustion gas in the roasting process of the lithium battery, the fluorine component having a high purity can not be recovered and the fluorine can not be reused. In the treatment method (C), the treatment of the recovered electrolytic solution becomes a problem. Since the electrolytic solution contains a flammable organic solvent and the fluorine compound in the electrolytic solution reacts with water to generate toxic hydrogen fluoride, a safe treatment is required. In the treatment method (D), the treatment of the post-cleaning liquid containing the organic solvent becomes a problem. In the above treatment method (E), high-temperature acid is added to the post-cleaning solution to decompose LiPF 6 into phosphoric acid and fluorine, and calcium hydroxide is added to this to form calcium fluoride and calcium phosphate. It is a mixture of Ca and phosphoric acid Ca, so reuse is difficult.
본 발명은, 종래의 처리 방법에 있어서의 상기 문제를 해결한 것으로, 휘발성을 갖는 불소 화합물 (LiPF6 등) 및 유기 용매를 함유하는 전해액을 안전하게 처리하는 방법을 제공하는 것을 목적으로 한다.The present invention solves the above problems in the conventional treatment method, and aims to provide a method for safely treating a volatile fluorine compound (LiPF 6 or the like) and an electrolytic solution containing an organic solvent.
본 발명은 이하의 구성으로 이루어지는 불소 함유 전해액의 처리 방법이다.The present invention is a method for treating a fluorine-containing electrolytic solution having the following constitution.
[1] 불소 함유 전해액에 함유되는 휘발 성분을 가열하여 기화시켰을 때의 기화 잔류액에 알칼리를 첨가하여 중화하는 처리 방법으로서, 상기 불소 함유 전해액이, 폐전지 중의 전해액, 폐전지를 절단 내지 파쇄한 상태의 전해액, 사용 전의 전해액, 또는 폐전지로부터 발출된 전해액이고, 상기 전해액의 기화 잔류액에 알칼리를 첨가하여 중화하는 불소 함유 전해액의 처리 방법.[1] A treatment method for neutralizing a vaporized residual liquid obtained by heating and vaporizing a volatile component contained in a fluorine-containing electrolytic solution by adding alkali, characterized in that the fluorine-containing electrolytic solution is a solution obtained by dissolving an electrolytic solution in a waste battery, The electrolytic solution before use, the electrolytic solution before use, or the electrolytic solution discharged from the spent battery, and adding the alkali to the vaporization residue of the electrolytic solution to neutralize the electrolytic solution.
[2] 상기 전해액의 휘발 성분을 기화시킨 상기 폐전지의 파쇄 처리시에 알칼리를 첨가하여 중화 처리와 파쇄를 동시에 실시하는 상기 [1] 에 기재된 불소 함유 전해액의 처리 방법.[2] The method for treating a fluorine-containing electrolytic solution according to [1], wherein alkaline is added during the crushing treatment of the waste battery in which the volatile component of the electrolytic solution is vaporized to perform neutralization and crushing simultaneously.
[3] 상기 전해액의 휘발 성분을 기화시킨 상기 폐전지의 파쇄물에 알칼리를 첨가하여 중화하는 상기 [1] 에 기재된 불소 함유 전해액의 처리 방법.[3] The method for treating a fluorine-containing electrolytic solution according to [1], wherein alkaline is added to the pulverized product of the waste battery in which the volatile component of the electrolytic solution is vaporized to neutralize.
[4] 상기 휘발 성분이 기화된 기화 가스를 회수하고, 상기 기화 가스에 함유되는 불소 성분을 칼슘과 반응시켜 불화칼슘으로 하여 회수하는 상기 [1] 또는 상기 [2] 에 기재된 불소 함유 전해액의 처리 방법.[4] A process for treating a fluorine-containing electrolytic solution as described in [1] or [2], wherein the vaporized gas in which the volatile component is vaporized is recovered and the fluorine component contained in the vaporized gas is reacted with calcium to recover calcium fluoride Way.
[5] 상기 휘발 성분이 기화된 기화 가스를 회수하고, 상기 기화 가스에 함유되는 불소 성분을 칼슘과 반응시켜 불화칼슘으로 하여 회수하는 한편, 그 기화 가스를 냉각시켜 응축 포집하여, 유기 용매 성분을 회수하는 상기 [1] ∼ 상기 [3] 중 어느 하나에 기재된 불소 함유 전해액의 처리 방법.[5] A method of recovering vaporized gas in which vaporized components of vaporized components are vaporized, reacting fluorine components contained in the vaporized gas with calcium to recover calcium fluoride, while cooling the vaporized gas to collect and collect the organic solvent component A method for treating a fluorine-containing electrolytic solution according to any one of [1] to [3], wherein the fluorine-containing electrolytic solution is recovered.
본 발명의 처리 방법에 의하면, 전해액을 기화시켜 취출하므로, 폐전지를 냉동 내지 고온에서 연소시키지 않고 안전하게 처리할 수 있다.According to the treatment method of the present invention, since the electrolytic solution is vaporized and taken out, it is possible to safely treat the waste battery without burning it at high temperatures.
또, 기화 잔류액의 알칼리 처리에 의해 강산성의 기화 잔류액이 중화되므로, 전극의 부식이나 열화가 억제된다. 그 결과, 재이용에 적합한 재료를 회수할 수 있다. 또한 파쇄 작업이나 분별 작업 등을 안전하게 실시할 수 있고, 파쇄 장치나 선별 장치의 부식을 방지할 수 있다. 또, 이 알칼리 중화 처리는 기화 공정의 후에 실시되므로, 알칼리 중화 처리는 기화 공정에 영향을 주지 않는다. 또, 기화 잔류액에 알칼리를 첨가하여 중화함으로써, 기화 잔류액에 함유되어 있는 불소를 고정시킬 수 있다.Further, the alkaline treatment of the vaporization residue liquid neutralizes the strong acidic vaporization residue, so that the corrosion or deterioration of the electrode is suppressed. As a result, a material suitable for reuse can be recovered. Further, it is possible to safely carry out the crushing operation and the separating operation, and to prevent the corrosion of the crushing device and the sorting device. Further, since this alkali neutralization treatment is carried out after the vaporization step, the alkali neutralization treatment does not affect the vaporization step. In addition, fluorine contained in the vaporization residue can be fixed by adding alkali to the vaporization residue to neutralize it.
또한, 본 발명의 처리 방법에 의하면, 기화 가스로부터 불소를 순도가 높은 불화칼슘으로 하여 회수할 수 있다. 예를 들어, 순도 80 ％ 이상의 불화칼슘을 얻을 수 있다. 이 불화칼슘을 불산 제조의 원료 또는 시멘트 원료로서 재이용할 수 있다.Further, according to the treatment method of the present invention, fluorine can be recovered from the vaporized gas as calcium fluoride having a high purity. For example, calcium fluoride having a purity of 80% or more can be obtained. This calcium fluoride can be reused as a raw material for producing hydrofluoric acid or as a raw material for cement.
또, 회수된 유기 용매 성분을 연료 또는 대체 연료로서 이용할 수 있다. 본 발명의 처리 방법에 의해 회수된 유기 용매 성분은, 불소가 분리되어 있으므로, 연료로서 사용했을 때에 불화수소 등의 유해 물질이 발생하지 않아, 안전하게 사용 할 수 있다.Further, the recovered organic solvent component can be used as a fuel or an alternative fuel. Since the organic solvent component recovered by the treatment method of the present invention is separated from fluorine, harmful substances such as hydrogen fluoride are not generated when it is used as a fuel and can be safely used.
도 1 은, 본 발명의 실시형태의 처리 방법의 개략을 나타내는 공정도이다.
도 2 는, 실시예 2 의 XRD 도이다.BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a process diagram showing an outline of a processing method of an embodiment of the present invention. FIG.
2 is an XRD diagram of the second embodiment.
[구체적인 설명][Explanation]
이하, 본 발명의 일 실시형태를 구체적으로 설명한다. 또한, ％ 는 특별히 설명이 없는 한 질량 ％ 를 나타내고, ppm 은 질량ppm 을 나타낸다.Hereinafter, an embodiment of the present invention will be described in detail. In addition,% represents mass% unless otherwise stated, and ppm represents mass ppm.
본 실시형태의 처리 방법은, 불소 함유 전해액에 함유되는 휘발 성분을 가열하여 기화시켰을 때의 기화 잔류액에 알칼리를 첨가하여 중화하는 처리 방법으로서, 상기 불소 함유 전해액이, 폐전지 중의 전해액, 폐전지를 절단 내지 파쇄한 상태의 전해액, 사용 전의 전해액, 또는 폐전지로부터 발출된 전해액이고, 상기 전해액의 기화 잔류액에 알칼리를 첨가하여 중화하는 방법이다.The treatment method of the present embodiment is a treatment method for neutralizing a vaporized residual liquid obtained by heating and vaporizing a volatile component contained in a fluorine-containing electrolytic solution by adding alkali, wherein the fluorine-containing electrolytic solution contains an electrolytic solution and a waste battery An electrolytic solution in a cut or crushed state, an electrolytic solution before use, or an electrolytic solution extracted from a spent cell, and adding an alkali to the vaporized residue of the electrolytic solution to neutralize the solution.
본 실시형태의 처리 방법의 개략을 나타내는 공정도를 도 1 에 나타낸다.Fig. 1 shows a process chart schematically showing the processing method of the present embodiment.
본 실시형태의 처리 방법은, 리튬 전지 등에 사용되고 있는 전해액에 적용할 수 있다. 리튬 이온 전지 등에 사용되고 있는 전해액에는, 전해질의 불소 화합물과 유기 용매가 함유되어 있다. 불소 화합물은 주로 헥사플루오로인산리튬 (LiPF6) 이고, 유기 용매는 디메틸카보네이트 (DMC), 에틸메틸카보네이트 (EMC), 디에틸카보네이트 (DEC), 프로필렌카보네이트 (PC), 에틸렌카보네이트 (EC) 등의 탄산에스테르류이다. DMC, EMC, DEC 는 인화성 물질이다.The treatment method of the present embodiment can be applied to an electrolytic solution used in a lithium battery or the like. The electrolytic solution used in a lithium ion battery or the like contains a fluorine compound of an electrolyte and an organic solvent. Fluorine compounds are mainly lithium phosphate (LiPF 6) hexafluoropropane, the organic solvent is dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC), propylene carbonate (PC), ethylene carbonate (EC), etc. Of carbonic acid esters. DMC, EMC and DEC are flammable substances.
또, 본 실시형태의 처리 방법은, 이와 같은 불소 함유 전해액으로서, 폐전지 중의 전해액, 폐전지를 절단 내지 파쇄하여 얻어지는 전해액, 사용 전의 전해액, 또는 폐전지로부터 발출된 전해액 등을 기화 처리했을 때의 기화 잔류액에 알칼리를 첨가하여 중화하는 처리 방법이다.The treatment method of the present embodiment is characterized in that the electrolytic solution in the waste battery, the electrolytic solution obtained by cutting or crushing the waste battery, the electrolytic solution before use, the electrolytic solution withdrawn from the spent battery or the like is subjected to vaporization And the alkali is added to the residual liquid to neutralize it.
[기화 공정][Vaporization Process]
기화 공정에서는, 불소 함유 전해액에 함유되는 휘발 성분을 불소 함유 전해액을 가열함으로써 기화시킨다 (스텝 S1).In the vaporization step, the volatile component contained in the fluorine-containing electrolytic solution is vaporized by heating the fluorine-containing electrolytic solution (step S1).
폐전지 중의 전해액을 처리하는 경우, 먼저, 사용 완료된 폐전지를 방전한 후에 가열하여 전해액의 휘발 성분을 기화시킨다. 일반적으로, 전지에는 과잉의 내부압을 낮추기 위해서 안전 밸브가 형성되어 있으므로, 이 안전 밸브를 개구하여 관로를 접속하고, 그 폐전지를 가열하여 전해액에 함유되는 휘발 성분을 기화시키면 된다.In the case of treating the electrolytic solution in the waste battery, first, the used battery is discharged and then heated to vaporize the volatile component of the electrolytic solution. Generally, since a safety valve is formed in the battery to lower the excess internal pressure, the safety valve is opened to connect the pipe, and the volatile component contained in the electrolytic solution is vaporized by heating the waste battery.
또는, 폐전지를 절단 내지 파쇄하여 얻어진 전해액을 처리해도 된다. 이 경우, 절단 내지 파쇄된 폐전지는, 전지 내부의 전해액이 전극 재료와 함께 외부로 노출된 상태가 되므로, 전해액을 처리할 수 있다. 폐전지의 절단 또는 파쇄는, 전해액에 인화되지 않도록 불활성 가스 분위기에서 실시하면 된다.Alternatively, the electrolytic solution obtained by cutting or crushing the spent battery may be treated. In this case, the electrolytic solution can be treated because the cut or crushed waste battery is exposed to the outside together with the electrode material. The cutting or crushing of the waste battery may be performed in an inert gas atmosphere so as not to be ignited in the electrolytic solution.
본 실시형태의 처리 방법은, 사용 전의 전해액, 혹은 폐전지로부터 발출한 전해액에 대해서도 적용할 수 있다. 전해액을 폐전지로부터 발출하기 위해서는, 폐전지를 세정 용매로 세정하여 전해액을 추출한다. 세정 용매로서, 물 혹은 비점 150 ℃ 이하의 유기 용매를 사용할 수 있다. 또한, 전해액에 함유되는 탄산에스테르류를 회수하여, 세정 용매로서 재이용할 수 있다.The treatment method of the present embodiment can be applied to an electrolytic solution before use or an electrolytic solution discharged from a spent battery. In order to extract the electrolyte from the waste battery, the spent battery is rinsed with a cleaning solvent to extract the electrolyte solution. As the cleaning solvent, water or an organic solvent having a boiling point of 150 ° C or less can be used. In addition, the carbonic ester compounds contained in the electrolytic solution can be recovered and reused as a cleaning solvent.
이와 같은 기화 공정에서는, 전해액에 함유되는 유기 용매의 비점보다 높은 온도까지 전해액을 가열하여, 유기 용매의 휘발 성분을 기화시킨다. LiPF6 은 물과 공존 하에서 가열되면 분해되어, 불소 성분이 불화수소가 되어 기화된다.In such a vaporization step, the electrolytic solution is heated to a temperature higher than the boiling point of the organic solvent contained in the electrolytic solution to vaporize the volatile components of the organic solvent. LiPF 6 decomposes when heated in the presence of water, and the fluorine component becomes hydrogen fluoride and vaporizes.
안전 밸브를 개구하여 관로를 접속하여 휘발 성분을 기화시키는 경우, 전지 내부를 감압하여 전해액을 가열하면, 내부 온도가 높아지므로 휘발 성분이 기화되기 쉬워진다. 예를 들어, 전지 내부를 5 ㎪ 로 감압하여 80 ℃ ∼ 150 ℃ 로 가열하면, 대기압 환산 온도는 170 ℃ ∼ 251 ℃ 의 상태가 된다. 1 ㎪ ∼ 0.1 ㎪ 로 감압하여 80 ℃ ∼ 120 ℃ 로 가열해도 된다.When the safety valve is opened to connect the pipe to vaporize the volatile component, if the inside of the battery is decompressed and the electrolytic solution is heated, the internal temperature becomes high, so that the volatile component is easily vaporized. For example, when the inside of the battery is reduced to 5 하여 and heated to 80 캜 to 150 캜, the atmospheric pressure conversion temperature becomes 170 캜 to 251 캜. It may be heated to 80 ° C to 120 ° C under a reduced pressure of 1 to 0.1 ° C.
폐전지를 불활성 가스 분위기의 용기 내에서 절단 또는 파쇄한 경우에는, 그 용기인 채로 가열하여 휘발 성분을 기화시키면 된다. 또한, 이 용기의 내부를 감압하여 가열해도 된다.When the waste battery is cut or crushed in a container of an inert gas atmosphere, the volatile component may be vaporized by heating the container in the container. Further, the inside of the container may be heated under reduced pressure.
소량의 물이나 소량의 희박한 광산을 첨가한 전해액을 감압 하에서 가열함으로써, 하기 식 (1) 과 같이, LiPF6 은 물과 순차적으로 반응시켜 인산과 불화수소로 가수 분해한다. 이로써, LiPF6 의 분해에 의한 기화를 촉진할 수 있다.LiPF 6 reacts with water in sequence to hydrolyze it with phosphoric acid and hydrogen fluoride, as shown in the following formula (1), by heating an electrolytic solution to which a small amount of water or a small amount of lean mine is added under reduced pressure. Thereby, vaporization by decomposition of LiPF 6 can be promoted.
[화학식 1][Chemical Formula 1]
[알칼리 중화 처리 공정][Alkaline neutralization treatment step]
폐전지의 기화 처리 (스텝 S1) 후에는, 소량의 불소 화합물이나 유기 용매가 기화되지 않고, 기화 잔류액으로서 잔류하는 경우가 많다. 일례로서, 전해액의 약 30 ％ 가 잔류한다.After the vaporization treatment of the waste battery (step S1), a small amount of the fluorine compound or the organic solvent is not vaporized and remains as a vaporization residue in many cases. As an example, about 30% of the electrolytic solution remains.
이 기화 잔류액은, 강산성의 액체인 인산 화합물, 불소 화합물, 리튬 화합물 및 고비등점의 탄산에스테르류를 함유한다. 이 기화 잔류액이 전지 재료에 부착되어, 재료의 부식이나 열화를 일으킨다. 폐전지의 전해액을 세정 용매로 추출하는 경우에도, 이들의 불소 화합물이나 유기 용매가 잔류할 가능성이 있다.This vaporization residue contains a phosphoric acid compound, a fluorine compound, a lithium compound, and a high boiling point carbonate ester, which are strongly acidic liquids. This vaporization residue adheres to the battery material, causing corrosion or deterioration of the material. Even when the electrolytic solution of the waste battery is extracted with a cleaning solvent, these fluorine compounds and organic solvents may remain.
본 실시형태의 처리 방법에서는, 기화 처리 후에 잔류한 기화 잔류액에 알칼리를 첨가하여 중화한다 (스텝 S2). 구체적으로는, 기화 처리 후에 폐전지 내부에 잔류하여 부착된 액분 (부착 잔류액), 또는 세정 후 액을 기화 처리했을 때의 잔류액 (세정 후 기화 잔류액) 에 알칼리를 첨가하고 중화하여, 무해화한다. 또한, 중화 후의 잔류액의 pH 는 4 이상 10 이하인 것이 바람직하고, 6 이상 8 이하인 것이 보다 바람직하다.In the treatment method of the present embodiment, alkali is added to the vaporization residue remaining after the vaporization treatment to neutralize (Step S2). Concretely, alkali is added to the residual liquid (adhesion residual liquid) remaining in the waste battery after the vaporization treatment, or the residual liquid (vaporized residual liquid after cleaning) after vaporization treatment of the liquid after cleaning, and neutralized, I am angry. The pH of the residue after neutralization is preferably 4 or more and 10 or less, more preferably 6 or more and 8 or less.
기화 잔류액에 첨가하는 알칼리로서, 가성 소다 (NaOH), Ca 계 중화제 [Ca(OH)2, CaCO3, CaO], Mg 계 중화제 [(MgO, Mg(OH)2] 등을 사용할 수 있다. 혹은, 이들 혼합물을 사용해도 된다. Ca 계 중화제는 저렴하고, 또 Ca 계 중화제를 사용하면 불소나 인을 난용성염으로서 고정화시킬 수 있기 때문에 유리하다.(NaOH), a Ca-based neutralizing agent [Ca (OH) 2 , CaCO 3 , CaO], a Mg-based neutralizing agent [(MgO, Mg (OH) 2 ] and the like may be used as an alkali to be added to the vaporization residue. The Ca-based neutralizing agent is advantageous because it is inexpensive and, if a Ca-based neutralizing agent is used, the fluorine and phosphorus can be immobilized as a sparingly soluble salt.
이들 알칼리는, 분말, 용액, 또는 슬러리의 상태로 사용할 수 있다. 용액 또는 슬러리로 사용하는 경우에는, 알칼리의 농도는 용액 또는 슬러리의 전체 중량의 0.1 ∼ 20 ％ 가 바람직하다. 알칼리의 사용량은, 폐전지에 함유되는 전해액 중량에 대해 0.5 ∼ 30 ％ 가 바람직하다.These alkalis can be used in the form of powders, solutions, or slurries. When used as a solution or slurry, the concentration of alkali is preferably 0.1 to 20% of the total weight of the solution or slurry. The amount of alkali to be used is preferably 0.5 to 30% based on the weight of the electrolytic solution contained in the waste battery.
폐전지의 기화 잔류액에 알칼리를 첨가하여 중화하면, 기화 잔류액에 함유되는 불소를 고정화 (고형화) 시킬 수 있다. 예를 들어, 기화 잔류액에 NaOH 를 첨가하여 중화하면, NaF, NaHF2, LiF 등을 함유하는 침전이 생긴다.Fluorine contained in the vaporization residue can be fixed (solidified) by adding alkali to the vaporization residue of the waste battery and neutralizing it. For example, when NaOH is added to the vaporization residue to neutralize, a precipitate containing NaF, NaHF 2 , LiF or the like is formed.
상기와 같은 기화 잔류액 (세정 후 기화 잔류액 및 부착 잔류액을 포함한다)에 알칼리를 첨가하여 중화하여, 무해화함으로써, 전극의 부식이나 열화를 억제하여, 재이용에 적합한 재료를 회수할 수 있다. 또, 파쇄 작업이나 분별 작업 등을 안전하게 실시할 수 있어, 파쇄 장치나 선별 장치의 부식을 방지할 수 있다. 또한, 상기 잔류액에 알칼리를 첨가하여 중화함으로써, 잔류액에 함유되어 있는 불소를 고정시킬 수 있다.Alkali is added to the vaporization residue liquid (including the vaporization residue and the adhesion residue after cleaning) to neutralize and neutralize the electrode, thereby preventing corrosion or deterioration of the electrode and recovering a material suitable for reuse . In addition, the crushing operation and the separating operation can be performed safely, and corrosion of the crushing device and the sorting device can be prevented. Further, by adding alkali to the residual liquid and neutralizing it, the fluorine contained in the residual liquid can be fixed.
또한, 통상, 전해액이 발출된 폐전지는 파쇄되고, 그것에 의해 얻어진 파쇄물은 사용 재료마다 분별되어 재자원화된다. 알칼리는, 도 1 에 있어서 폐전지의 파쇄 처리 전에 첨가되고 있지만, 폐전지의 파쇄 처리 후나 파쇄 처리 중에 첨가되어도 된다. 즉, 폐전지를 파쇄 처리하기 전, 또는 폐전지의 파쇄 처리시에 알칼리를 첨가하여, 중화 처리와 파쇄를 동시에 실시해도 되고, 혹은 폐전지의 파쇄물에 알칼리를 첨가하여 중화해도 된다.In addition, normally, the waste battery from which the electrolytic solution is taken out is crushed, and the crushed material obtained thereby is separated and recycled for each material used. The alkali is added before the crushing process of the waste battery in Fig. 1, but may be added after the crushing process of the waste battery or during the crushing process. That is, the neutralization treatment and the crushing may be simultaneously performed by adding alkali before the crushing treatment of the waste battery or during the crushing treatment of the waste battery, or the crushing of the waste battery may be neutralized by adding alkali.
[회수 공정][Recovery process]
폐전지의 전해액의 기화 처리, 또는 세정 추출한 전해액의 기화 처리에 의해 기화된 가스 (기화 가스) 를 회수하고, 그 기화 가스에 함유되는 불소 성분을 칼슘과 반응시켜 불화칼슘으로 하여 회수할 수 있다 (스텝 S3). 또한 불소를 불화칼슘으로 하여 회수하는 한편, 그 기화 가스를 냉각시켜 응축함으로써 포집하여, 유기 용매 성분을 함유하는 응축액을 회수할 수 있다 (스텝 S4).The vaporized gas (vaporized gas) is recovered by the vaporization treatment of the electrolytic solution of the waste battery or the vaporization treatment of the electrolytic solution extracted by washing, and the fluorine component contained in the vaporized gas is reacted with calcium to recover calcium fluoride ( Step S3). In addition, fluorine is recovered as calcium fluoride, and the vaporized gas is cooled and condensed to be collected, thereby recovering the condensate containing the organic solvent component (step S4).
구체적으로는, 기화된 가스를 수랭 트랩에 도입하여, 가스 중의 유기 용매와 불화수소를 포집한다. 이들은 수상과 유기상의 2 층으로 분리된다. 수상에는 기화 가스 중의 불소 성분이 함유되어 있고, 대체로 pH 2 이하의 산성이다. 이 수상 (불소 함유수) 에 칼슘 화합물 (탄산칼슘, 소석회, 생석회 등) 을 첨가하여 중화하고, 액 중의 불소와 칼슘을 반응시켜 불화칼슘을 침전시킨다. 이 불화칼슘을 고액 분리하여 회수한다 (스텝 S3).Specifically, the vaporized gas is introduced into the water-cooling trap to collect the organic solvent and hydrogen fluoride in the gas. They are separated into two layers, an aqueous phase and an organic phase. The water phase contains a fluorine component in the vaporized gas and is generally acidic with a pH of 2 or less. A calcium compound (calcium carbonate, slaked lime, quick lime, etc.) is added to the water phase (fluorine-containing water) to neutralize the fluorine and calcium in the solution to precipitate calcium fluoride. This calcium fluoride is recovered by solid-liquid separation (step S3).
기화된 유기 용매에 비해 물 (불소 함유수) 이 미량일 때에는, 유기 용매와 불화수소가 상호 용해되어 유기상만이 된다. 이 유기상에 칼슘 화합물을 첨가해도 되고, 첨가에 의해 생성된 불화칼슘을 고액 분리함으로써, 불소를 제거한 유기상을 회수할 수 있다. 또, 기화 가스를 칼슘 충전층에 도입하여 불화칼슘을 생성시키고, 그 충전층을 통과한 가스를 냉각시켜 응축액으로 하여, 유기 용매를 회수해도 된다 (스텝 S4).When the amount of water (fluorine-containing water) is smaller than that of the vaporized organic solvent, the organic solvent and hydrogen fluoride mutually dissolve to form only the organic phase. A calcium compound may be added to the organic phase, and the fluorine-removed organic phase can be recovered by solid-liquid separation of the calcium fluoride produced by the addition. In addition, vaporized gas may be introduced into the calcium-filled layer to generate calcium fluoride, and the gas passing through the packed layer may be cooled to be a condensate to recover the organic solvent (step S4).
실시예Example
다음으로, 본 발명의 실시형태에 관련된 실시예를 이하에 나타낸다. 또한, 액의 pH 는 유리 전극법에 의해 분석하였다. 구체적으로는, Horiba 제조의 pH 전극 9625-10D 를 pH 전극으로서 사용하고, 측정 대상액의 온도를 20 ℃ 로 하여 pH 를 측정하였다. 또, 불소 농도는 불화물 이온 전극법에 의해 분석하였다. 구체적으로는, 측정 대상액 100 ㎖ 에 이온 강도 조정제 (칸토 화학사 제조 TISAB (A total ionic strength adjustment buffer)) 를 5 ㎖ 첨가하여, 액온 20 ℃ 에서 불소 농도를 측정하였다. 불화물 이온 전극으로서 Horiba 제조의 불화물 이온 전극 6561-10C 를 사용하였다.Next, embodiments related to the embodiment of the present invention are described below. The pH of the solution was analyzed by a glass electrode method. Specifically, a pH electrode 9625-10D manufactured by Horiba was used as a pH electrode, and the pH of the liquid to be measured was measured at 20 占 폚. The fluorine concentration was analyzed by the fluoride ion electrode method. Specifically, 5 ml of an ionic strength adjusting agent (TISAB (A total ionic strength adjustment buffer) manufactured by Kanto Chemical Co., Ltd.) was added to 100 ml of the measurement target liquid, and the fluorine concentration was measured at a liquid temperature of 20 캜. Fluoride ion electrode 6561-10C manufactured by Horiba was used as the fluoride ion electrode.
[실시예 1][Example 1]
리튬 이온 폐전지 (전해액 100 ㎖ 함유) 를 방전시킨 후에 안전 밸브를 제거하고, 그 개구로부터 물 20 g 을 첨가하였다. 상기 개구에 관로를 접속하고, 그 폐전지를 20 ㎪ 의 압력 하에서, 120 ℃ 에서 2 시간 가열하여 전지 내부의 전해액을 기화시켰다. 그 후, 폐전지를 3 ㎝ 이하로 파쇄하였다. 이 파쇄물 전체에 기화 잔류액이 부착되어 있었다. 이 파쇄물 100 g 에 Ca(OH)2 를 5 g (파쇄물 중량에 대해 5 ％) 첨가하여 10 분간 혼합하였다. 이 혼합물을 1 시간 물에 침지시켰다. 침지 후의 물의 pH 는 10.2 이고, 불소 농도는 31 ppm 이었다.After discharging the lithium ion scavenging cell (containing 100 ml of the electrolytic solution), the safety valve was removed, and 20 g of water was added from the opening. A pipe was connected to the opening, and the spent battery was heated at 120 캜 for 2 hours under a pressure of 20 ㎪ to vaporize the electrolytic solution in the battery. Thereafter, the waste battery was crushed to 3 cm or less. The vaporized residue remained attached to the whole of the crushed product. 5 g of Ca (OH) 2 (5% based on the weight of the crushed product) was added to 100 g of the crushed product and mixed for 10 minutes. This mixture was immersed in water for 1 hour. The pH of the water after immersion was 10.2, and the fluorine concentration was 31 ppm.
[실시예 2][Example 2]
리튬 이온 폐전지 (전해액 100 ㎖ 함유) 를 방전한 후에 안전 밸브를 제거하고, 세정 용매로서 DEC 와 EMC 의 혼합 용매 (1：1) 100 ㎖ 를 주입한 후에 배출 한다는 세정 조작을 5 회 반복하여 전해액을 추출하였다. 회수한 세정 후 액에 물 20 g 을 첨가하고, 20 ㎪ 의 압력 하에서, 120 ℃ 에서 2 시간 가열하여 휘발 성분을 기화시켰다. 기화 잔류액은 점성이 높은 액체이고, 중량은 34.5 g, pH 1.8 이었다. 이 기화 잔류액에 24 wt％ NaOH 수용액을 10 ㎖ 첨가한 결과, 격렬하게 반응하여 백색 침전을 생성하여 잔류액은 흰 겔상이 되었다. 이 겔상물의 pH 는 8.3 이고, 중량은 42.3 g 이었다. 이 흰 겔상물을 진공 건조 처리하여, XRD (X 선 회절) 측정을 실시하였다. 얻어진 XRD 도 (X 선 스펙트럼도) 를 도 2 에 나타낸다. XRD 도에 나타내는 바와 같이, 그 겔상물에는 NaF, NaHF, LiF 가 함유되어 있어, 잔류액의 불소가 고정된 것이 확인되었다.After discharging the lithium ion battery (containing 100 ml of electrolyte), the safety valve was removed, and 100 ml of a mixed solvent of DEC and EMC (1: 1) as a washing solvent was injected and discharged. . 20 g of water was added to the recovered washed liquid, and the volatile component was vaporized by heating at 120 캜 for 2 hours under a pressure of 20.. The vaporization residue was a viscous liquid with a weight of 34.5 g and a pH of 1.8. When 10 ml of a 24 wt% NaOH aqueous solution was added to the vaporization residue, the reaction was vigorous to produce a white precipitate, which resulted in a white gel phase. The gel had a pH of 8.3 and a weight of 42.3 g. The white gel product was subjected to vacuum drying treatment, and XRD (X-ray diffraction) measurement was carried out. The obtained XRD diagram (X-ray spectrum diagram) is shown in Fig. As shown in the XRD diagram, it was confirmed that the gel product contained NaF, NaHF, LiF, and fluorine of the residual liquid was fixed.
[실시예 3][Example 3]
실시예 1 에서 기화된 가스를 냉각관 (4 ℃), 응축 트랩의 순서로 유도하여, 응집액 70 ㎖ 를 회수하였다. 이 수상의 불소 농도는 50200 g/ℓ, pH 1.2 였다. 이것에 탄산칼슘 9.30 g 을 첨가하여 침전을 생성시켰다. 회수된 침전 성분을 분말 X 선 회절에 의해 분석하여, 불화칼슘인 것을 확인하였다. 불화칼슘의 회수량은 7.49 g 이고, 순도 87 ％ 였다. 한편, 유기 성분을 분석한 결과, 용액의 성분은 DMC, MEC, DEC 였다.The gas vaporized in Example 1 was introduced in the order of a cooling tube (4 캜) and a condensation trap in order to collect 70 ml of the coagulating solution. The fluorine concentration of this aqueous phase was 50200 g / L, pH 1.2. To this was added 9.30 g of calcium carbonate to form a precipitate. The recovered precipitate component was analyzed by powder X-ray diffraction to confirm that it was calcium fluoride. The recovered amount of calcium fluoride was 7.49 g and the purity was 87%. On the other hand, analysis of the organic components revealed that the components of the solution were DMC, MEC, and DEC.
[비교예 1][Comparative Example 1]
실시예 1 과 동일한 폐전지에 물 20 g 을 첨가하고, 그 폐전지를 20 ㎪ 의 압력 하에서, 120 ℃ 에서 2 시간 가열하여 전지 내부의 전해액을 기화시켰다. 그 후, 폐전지로부터 건조가 완료된 베어셀을 취출하여 3 ㎝ 이하로 파쇄 절단하였다. 이 파쇄물 100 g 을 1 시간 물에 침지하였다. 침지 후의 물의 pH 는 2.3 이고, 불소 농도는 410 ppm 이었다.20 g of water was added to the same waste battery as in Example 1, and the spent battery was heated at 120 캜 for 2 hours under a pressure of 20 ㎪ to vaporize the electrolytic solution in the battery. Thereafter, the dried bare cell was taken out from the waste battery and crushed and cut to 3 cm or less. 100 g of the lysate was immersed in water for 1 hour. The pH of the water after immersion was 2.3 and the fluorine concentration was 410 ppm.
이상, 본 발명의 바람직한 실시예를 설명했지만, 본 발명은 이 실시예에 한정되는 경우는 없다. 본 발명의 취지를 일탈하지 않는 범위에서, 구성의 부가, 생략, 치환 및 그 밖의 변경이 가능하다. 본 발명은 전술한 설명에 의해 한정되는 경우는 없고, 첨부한 청구의 범위에 의해서만 한정된다.Although the preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other modifications of the configuration are possible without departing from the spirit of the present invention. The present invention is not limited by the foregoing description, but is limited only by the appended claims.
산업상 이용가능성Industrial availability
본 발명의 불소 함유 전해액의 처리 방법에 의하면, 불소 화합물 및 유기 용매를 함유하는 전해액을 안전하게 처리할 수 있다. 이로써, 불소 함유 전해액을 함유하는 리튬 전지를 안전하게 처리할 수 있다.According to the method for treating a fluorine-containing electrolytic solution of the present invention, an electrolytic solution containing a fluorine compound and an organic solvent can be safely treated. Thereby, the lithium battery containing the fluorine-containing electrolytic solution can be safely treated.
S1 : 기화 공정
S2 : 알칼리 첨가 공정
S3 : 불소 고정 공정
S4 : 유기 용매 성분 회수 공정S1: vaporization process
S2: Alkali addition process
S3: Fluorine fixing process
S4: Organic solvent component recovery process
Claims (5)
상기 불소 함유 전해액이, 폐전지 중의 전해액, 폐전지를 절단 내지 파쇄한 상태의 전해액, 사용 전의 전해액, 또는 폐전지로부터 발출된 전해액이고, 상기 전해액의 기화 잔류액에 알칼리를 첨가하여 중화하는, 불소 함유 전해액의 처리 방법.A treatment method for neutralizing a volatile component contained in a fluorine-containing electrolytic solution by adding alkali to a vaporized residual liquid which is vaporized by heating,
Wherein the fluorine-containing electrolytic solution is an electrolytic solution in a waste battery, an electrolytic solution in a state in which a waste battery is cut or broken, an electrolytic solution before use, or an electrolytic solution extracted from a waste battery, and the solution is neutralized by adding alkali to the vaporization residue of the electrolytic solution A method for treating an electrolytic solution.
상기 전해액의 휘발 성분을 기화시킨 상기 폐전지의 파쇄 처리시에 알칼리를 첨가하여 중화 처리와 파쇄를 동시에 실시하는, 불소 함유 전해액의 처리 방법.The method according to claim 1,
Wherein the neutralization treatment and the crushing are simultaneously carried out by adding alkali in the pulverizing treatment of the waste battery in which the volatile component of the electrolytic solution is vaporized.
상기 전해액의 휘발 성분을 기화시킨 상기 폐전지의 파쇄물에 알칼리를 첨가하여 중화하는, 불소 함유 전해액의 처리 방법.The method according to claim 1,
Wherein the pulverized product of the waste battery in which the volatile component of the electrolytic solution is vaporized is neutralized by adding alkali.
상기 휘발 성분이 기화된 기화 가스를 회수하고, 상기 기화 가스에 함유되는 불소 성분을 칼슘과 반응시켜 불화칼슘으로 하여 회수하는, 불소 함유 전해액의 처리 방법.3. The method according to claim 1 or 2,
And recovering the vaporized gas from which the volatile component has vaporized and recovering calcium fluoride by reacting the fluorine component contained in the vaporized gas with calcium.
상기 휘발 성분이 기화된 기화 가스를 회수하고, 상기 기화 가스에 함유되는 불소 성분을 칼슘과 반응시켜 불화칼슘으로 하여 회수하는 한편, 그 기화 가스를 냉각시켜 응축 포집하여, 유기 용매 성분을 회수하는, 불소 함유 전해액의 처리 방법.
4. The method according to any one of claims 1 to 3,
And recovering the vaporized gas in which the volatile component is vaporized, recovering the fluorine component contained in the vaporized gas as calcium fluoride by reacting with calcium, condensing and collecting the vaporized gas to collect the organic solvent component, A method for treating a fluorine-containing electrolytic solution.
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