JP2015183292A - Recovery method of cobalt and nickel - Google Patents
Recovery method of cobalt and nickel Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 146
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052803 cobalt Inorganic materials 0.000 title claims abstract description 89
- 239000010941 cobalt Substances 0.000 title claims abstract description 89
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 73
- 238000011084 recovery Methods 0.000 title claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000010949 copper Substances 0.000 claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 claims abstract description 42
- 239000011572 manganese Substances 0.000 claims abstract description 42
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002244 precipitate Substances 0.000 claims abstract description 33
- 150000004763 sulfides Chemical class 0.000 claims abstract description 14
- BWFPGXWASODCHM-UHFFFAOYSA-N Copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims abstract description 13
- WNROFYMDJYEPJX-UHFFFAOYSA-K Aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- NUJOXMJBOLGQSY-UHFFFAOYSA-N Manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 229910000468 manganese oxide Inorganic materials 0.000 claims abstract description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese(II,III) oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 49
- HKZLPVFGJNLROG-UHFFFAOYSA-M Silver chloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- 238000000605 extraction Methods 0.000 claims description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims description 12
- 230000033116 oxidation-reduction process Effects 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 239000003929 acidic solution Substances 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 238000002386 leaching Methods 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 230000002378 acidificating Effects 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 13
- 230000001590 oxidative Effects 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000000638 solvent extraction Methods 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- NHYCGSASNAIGLD-UHFFFAOYSA-N chlorine monoxide Inorganic materials Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N HF Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N Hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M Sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- PQXKHYXIUOZZFA-UHFFFAOYSA-M Lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- AXPLOJNSKRXQPA-UHFFFAOYSA-N Lithium hexafluorophosphate Chemical compound [Li+].F[P-](F)(F)(F)(F)F AXPLOJNSKRXQPA-UHFFFAOYSA-N 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N Sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001376 precipitating Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L Cobalt(II) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K Lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L Nickel(II) sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical compound [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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
Abstract
Description
本発明は、コバルトおよびニッケルと共に銅、アルミニウム、マンガンを含む溶液からコバルトおよびニッケルを効率よく回収する方法に関する。本発明の回収方法は、リチウムイオン二次電池から分別した正極材活物質を鉱酸等で処理をした有価金属浸出液から、コバルトおよびニッケルを回収する方法として最適である。 The present invention relates to a method for efficiently recovering cobalt and nickel from a solution containing copper, aluminum and manganese together with cobalt and nickel. The recovery method of the present invention is optimal as a method for recovering cobalt and nickel from a valuable metal leachate obtained by treating a positive electrode active material separated from a lithium ion secondary battery with a mineral acid or the like.
リチウムイオン二次電池は、負極材と正極材とを、多孔質のポリプロピレン等のセパレータで分画し層状に重ね、六フッ化リン酸リチウム（LiPF6）等の電解質および電解液と共にアルミニウムやステンレス等のケースに封入して形成されている。 Lithium ion secondary batteries are made by separating the negative electrode material and the positive electrode material with a separator such as porous polypropylene, and stacking them in layers. Aluminum and stainless steel together with an electrolyte such as lithium hexafluorophosphate (LiPF 6 ) and an electrolytic solution are used. It is formed by enclosing in a case such as.
上記リチウムイオン二次電池の負極材は銅等の負極集電体に黒鉛等の負極材活物質を塗布して形成されており、正極材はアルミニウム等の正極集電体にマンガン酸リチウム、コバルト酸リチウム、ニッケル酸リチウム等の正極活物質を塗布して形成されている。 The negative electrode material of the lithium ion secondary battery is formed by applying a negative electrode material active material such as graphite to a negative electrode current collector such as copper, and the positive electrode material is formed of lithium manganate or cobalt on a positive electrode current collector such as aluminum. It is formed by applying a positive electrode active material such as lithium oxide or lithium nickelate.
このようにリチウムイオン二次電池の電極材にはリチウム、コバルト、ニッケル等の有価金属が多く含まれているので、有価金属の再利用を図るために、廃リチウムイオン二次電池からコバルト等の有価金属を回収する方法が知られている。例えば、正極活物質を硫酸に溶解してスラリーにし、該スラリーに過酸化水素水を添加して、濾液にリチウム、コバルト、ニッケルを含有させ、残渣にマンガンを含有させて分離する回収方法が知られている（特許文献１：特開２０１３−１９４３１５号公報）。また、正極材活物質を物理的に選別した後に硫酸等の鉱酸で浸出し、溶媒抽出によってコバルト等を回収する方法が知られている。 As described above, since the electrode material of the lithium ion secondary battery contains a lot of valuable metals such as lithium, cobalt, nickel, etc., in order to recycle the valuable metals, A method for recovering valuable metals is known. For example, a recovery method is known in which a positive electrode active material is dissolved in sulfuric acid to form a slurry, hydrogen peroxide water is added to the slurry, lithium, cobalt, nickel is added to the filtrate, and manganese is separated into the residue. (Patent Document 1: JP 2013-194315 A). Further, a method is known in which a positive electrode material active material is physically selected and then leached with a mineral acid such as sulfuric acid, and cobalt or the like is recovered by solvent extraction.
しかし、正極材活物質の酸浸出液には、活物質の主成分であるマンガン、コバルト、ニッケル、およびリチウムのほか、集電体である銅やアルミニウム、電解質である六フッ化リン酸リチウムやこれが加水分解して生成したフッ酸やリン酸が含まれており、特許文献１の方法では濾液や残渣に不純物が多く含まれることになり、コバルトやニッケルの回収手段として溶媒抽出を利用する場合に抽出効果が低い。 However, the acid leaching solution of the positive electrode active material includes manganese, cobalt, nickel, and lithium as main components of the active material, copper and aluminum as the current collector, lithium hexafluorophosphate as the electrolyte, and this. Hydrofluoric acid and phosphoric acid produced by hydrolysis are contained, and in the method of Patent Document 1, a large amount of impurities are contained in the filtrate and residue. When solvent extraction is used as a means for recovering cobalt and nickel, Extraction effect is low.
例えば、抽出剤としてリン酸系酸性抽出剤（PC-88A等）を用いると、浸出液中のアルミニウム、銅、マンガンがコバルトよりも先に抽出され、コバルトが十分に抽出されない。そこで、コバルトの抽出効果を高める方法として、コバルト水溶液に硫化剤を添加して銅を硫化銅沈澱にして分離し、この脱銅後、酸化剤を添加してマンガンを酸化物にして沈澱分離する脱マンガンを行う精製方法が知られている（特許文献２：特開２００４−２８５３６８号公報）。しかし、リチウムイオン二次電池の電極材にはアルミニウムやフッ化物が含まれており、この精製方法では十分に不純物を除去することができない。 For example, when a phosphoric acid-based acidic extractant (such as PC-88A) is used as the extractant, aluminum, copper, and manganese in the leachate are extracted before cobalt, and cobalt is not sufficiently extracted. Therefore, as a method for enhancing the extraction effect of cobalt, a sulfurizing agent is added to an aqueous cobalt solution to separate copper into copper sulfide, and after this copper removal, an oxidizing agent is added to convert manganese into an oxide to separate. A purification method for performing demanganese is known (Patent Document 2: Japanese Patent Application Laid-Open No. 2004-285368). However, the electrode material of the lithium ion secondary battery contains aluminum and fluoride, and this purification method cannot sufficiently remove impurities.
一方、コバルト、ニッケルと共にアルミニウム、マンガンを含む硫酸酸性溶液から溶媒抽出によってコバルトおよびニッケルと、アルミニウムおよびマンガンとを分離する方法が知られている（特許文献３：特開２０１３−７６１０８号公報）。しかし、この方法は溶媒抽出によって脱アルミニウムおよび脱マンガンを行う方法であるため、コストが嵩む問題がある。さらに、抽出後に溶媒からアルミニウムおよびマンガンを溶離する処理が必要になる。 On the other hand, a method is known in which cobalt and nickel are separated from aluminum and manganese by a solvent extraction from a sulfuric acid acidic solution containing aluminum and manganese together with cobalt and nickel (Patent Document 3: JP 2013-76108 A). However, since this method is a method in which dealumination and demanganese are performed by solvent extraction, there is a problem that costs increase. Furthermore, a process of eluting aluminum and manganese from the solvent after extraction is required.
また、リチウムイオン二次電池は自動車等への利用が進むにつれて大型化しており、大型の電池は電解質の量も多いのでこれを完全に除去することは難しく、選別された電極材に電解質が付着して回収される。これを浸出して湿式処理を行う際に付着している電解質の加水分解反応が進み、有害なフッ化水素や、リン酸リチウム、フッ化リチウムなどが生成し、これが共存金属と沈殿を生成して溶媒抽出の妨げになる。また、フッ素については排水基準が定められているため、排水中のフッ素濃度を低減する処理が必要になる。 In addition, lithium ion secondary batteries are becoming larger as they are used in automobiles, etc., and since large batteries have a large amount of electrolyte, it is difficult to completely remove them, and the electrolyte adheres to the selected electrode material. And recovered. When the wet process is carried out by leaching this, the hydrolysis reaction of the attached electrolyte proceeds, generating harmful hydrogen fluoride, lithium phosphate, lithium fluoride, etc., which generate coexisting metals and precipitates. This hinders solvent extraction. Moreover, since the drainage standard is defined for fluorine, a treatment for reducing the fluorine concentration in the wastewater is required.
電解質に含まれるリンやフッ素を除去する方法として、リチウムイオン二次電池の正極活物質の酸性浸出液にカルシウム化合物、マグネシウム化合物、またはアルミニウム化合物などを添加して、これらのフッ化物ないしリン酸塩を生成させて分離する方法が知られている（特許文献４：特開２０１２−３６４１９号公報）。
しかし、溶液中のフッ素やリンを除去するためにカルシウムやマグネシウムまたはアルミニウムの化合物を添加するとこれらの処理量が多くなり、負担が増す問題がある。
As a method of removing phosphorus and fluorine contained in the electrolyte, a calcium compound, a magnesium compound, or an aluminum compound is added to the acidic leachate of the positive electrode active material of the lithium ion secondary battery, and these fluorides or phosphates are added. A method of generating and separating is known (Patent Document 4: JP 2012-36419 A).
However, when a compound of calcium, magnesium, or aluminum is added to remove fluorine or phosphorus in the solution, there is a problem that the amount of these treatments increases and the burden increases.
本発明は、従来のコバルトおよびニッケルの回収方法における上記問題を解決したものであり、コバルトおよびニッケルと共に銅、アルミニウム、マンガンを含む溶液から銅、アルミニウムおよびマンガンを沈澱処理によって効果的に分離し、コバルトおよびニッケルを効率よく回収する方法を提供する。 The present invention solves the above-mentioned problems in conventional methods for recovering cobalt and nickel, and effectively separates copper, aluminum and manganese from a solution containing copper, aluminum and manganese together with cobalt and nickel by precipitation treatment, A method for efficiently recovering cobalt and nickel is provided.
本発明によれば、以下の構成からなるコバルトおよびニッケルの回収方法が提供される。
〔１〕コバルトおよびニッケルと共に銅、アルミニウム、マンガンを含む酸性溶液に硫化物を加えて硫化銅を沈殿させ、該沈殿を分離する脱銅工程、脱銅後の溶液にアルカリを添加して水酸化アルミニウムを沈殿させ、該沈殿を分離する脱アルミニウム工程、脱アルミニウム溶液に酸化剤を添加してマンガン酸化物を沈殿させ、該沈殿を分離する脱マンガン工程、脱マンガン後の溶液からコバルトおよびニッケルを回収する工程を有することを特徴とするコバルトおよびニッケルの回収方法。
〔２〕コバルトおよびニッケルと共に銅、アルミニウム、マンガンを含む酸性溶液がリチウムイオン二次電池の正極活物質を鉱酸で浸出した液である上記[１]に記載するコバルトおよびニッケルの回収方法。
〔３〕脱銅工程において、上記酸性溶液の酸化還元電位(Ag/AgCl電極基準)が−１５〜１３５ｍＶになるように硫化物を添加し、ｐＨ０〜１の液性下で硫化銅を沈澱させる上記[１]または上記[２]に記載するコバルトおよびニッケルの回収方法。
〔４〕脱アルミニウム工程において、脱銅後の溶液にアルカリを添加してｐＨ４〜６の液性下で水酸化アルミニウムを沈殿させる共に溶液中のリンおよびフッ素を共沈させる上記[１]〜上記[３]の何れかに記載するコバルトおよびニッケルの回収方法。
〔５〕脱マンガン工程において、脱アルミニウム後の溶液に酸化剤を添加し、酸化還元電位(Ag/AgCl電極基準)９５０〜１０５０ｍＶ、およびｐＨ２.５以下の液性下でマンガン酸化物を沈殿させる上記[１]〜上記[４]の何れかに記載するコバルトおよびニッケルの回収方法。
〔６〕コバルトおよびニッケルを回収する工程において、脱マンガン後の溶液からリン酸系酸性抽出溶媒を用いてコバルトおよびニッケルを溶媒抽出して回収する上記[１]〜上記[５]の何れかに記載するコバルトおよびニッケルの回収方法。
According to the present invention, a method for recovering cobalt and nickel having the following constitution is provided.
[1] A copper removal step in which sulfide is added to an acidic solution containing copper, aluminum, and manganese together with cobalt and nickel to precipitate copper sulfide, and the precipitate is separated. A dealumination step for precipitating aluminum and separating the precipitate; an oxidizing agent is added to the dealumination solution to precipitate manganese oxide; a demanganese step for separating the precipitate; and cobalt and nickel from the solution after demanganese A method for recovering cobalt and nickel, comprising a step of recovering.
[2] The method for recovering cobalt and nickel according to the above [1], wherein the acidic solution containing copper, aluminum, and manganese together with cobalt and nickel is a liquid obtained by leaching the positive electrode active material of a lithium ion secondary battery with mineral acid.
[3] In the copper removal step, sulfide is added so that the oxidation-reduction potential (Ag / AgCl electrode standard) of the acidic solution is −15 to 135 mV, and copper sulfide is precipitated under the liquidity of pH 0-1. The method for recovering cobalt and nickel described in [1] or [2] above.
[4] In the dealumination step, alkali is added to the solution after copper removal to precipitate aluminum hydroxide under pH 4 to 6 and co-precipitate phosphorus and fluorine in the solution. [3] The method for recovering cobalt and nickel according to any one of [3].
[5] In the demanganese step, an oxidizing agent is added to the solution after dealumination, and manganese oxide is precipitated under liquidity of redox potential (Ag / AgCl electrode standard) 950 to 1050 mV and pH 2.5 or lower. The method for recovering cobalt and nickel according to any one of [1] to [4] above.
[6] In any of the above [1] to [5], in the step of recovering cobalt and nickel, cobalt and nickel are extracted from the solution after demanganese using a phosphoric acid acidic extraction solvent and recovered. Cobalt and nickel recovery methods described.
〔具体的な説明〕
本発明の方法は、コバルトおよびニッケルと共に銅、アルミニウム、マンガンを含む酸性溶液に硫化物を加えて硫化銅を沈殿させ、該沈殿を分離する脱銅工程、脱銅後の溶液にアルカリを添加して水酸化アルミニウムを沈殿させ、該沈殿を分離する脱アルミニウム工程、脱アルミニウム溶液に酸化剤を添加してマンガン酸化物を沈殿させ、該沈殿を分離する脱マンガン工程、脱マンガン後の溶液からコバルトおよびニッケルを回収する工程を有することを特徴とするコバルトおよびニッケルの回収方法である。
本発明の回収方法を図１に示す。
[Specific description]
In the method of the present invention, a sulfide is added to an acidic solution containing copper, aluminum, and manganese together with cobalt and nickel to precipitate copper sulfide, and a copper removal step for separating the precipitate is performed. An alkali is added to the solution after copper removal. A dealumination step for precipitating aluminum hydroxide and separating the precipitate; adding an oxidizing agent to the dealumination solution to precipitate manganese oxide; demanganese step for separating the precipitate; And a method for recovering cobalt and nickel, comprising the step of recovering nickel.
The recovery method of the present invention is shown in FIG.
コバルトおよびニッケルと共に銅、アルミニウム、マンガンを含む酸性溶液としては、例えば、リチウムイオン二次電池の電極材の活物質を物理的に選別し、硫酸等の鉱酸で浸出した液である。４０℃〜９０℃の４〜６規定鉱酸に電極材活物質を溶液のｐＨが０〜１になるように加えて溶解させる。溶液のｐＨが０未満になると脱アルミニウムで使用するアルカリの量が増え、ｐＨが１を超えると不溶解分が増加するので好ましくない。
なお、後の脱アルミニウム工程においてフッ素およびリンを共沈させるために、浸出液中のアルミニウム濃度は１〜２ｇ/Lが好ましい。
As an acidic solution containing copper, aluminum, and manganese together with cobalt and nickel, for example, an active material of an electrode material of a lithium ion secondary battery is physically selected and leached with a mineral acid such as sulfuric acid. An electrode material active material is added to 4 to 6 N mineral acid at 40 to 90 ° C. so that the pH of the solution is 0 to 1 and dissolved. When the pH of the solution is less than 0, the amount of alkali used for dealumination increases, and when the pH exceeds 1, the insoluble matter increases, which is not preferable.
In addition, in order to coprecipitate fluorine and phosphorus in the subsequent dealumination step, the aluminum concentration in the leachate is preferably 1 to 2 g / L.
〔脱銅工程〕
上記浸出液に硫化物を加えて硫化銅を沈澱させ、該沈殿を固液分離する。好ましくは、ｐＨ０〜１の上記酸浸出液に、酸化還元電位(ＯＲＰ：Ag/AgCl電極基準)が−１５〜１３５ｍＶになるように、好ましくはＯＲＰが０〜５０ｍＶになるように、硫化物を添加して硫化銅を沈澱させる。ＯＲＰが−１５ｍＶ未満ではコバルトの硫化物が生成し、１３５ｍＶを上回ると硫化銅の生成が不十分になる。硫化物としては硫化水素、水硫化物などを用いることができる。
[Copper removal process]
Sulfide is added to the leachate to precipitate copper sulfide, and the precipitate is separated into solid and liquid. Preferably, sulfide is added to the acid leaching solution having a pH of 0 to 1 so that the oxidation-reduction potential (ORP: Ag / AgCl electrode standard) is -15 to 135 mV, and preferably ORP is 0 to 50 mV. To precipitate copper sulfide. If the ORP is less than −15 mV, cobalt sulfide is generated, and if it exceeds 135 mV, copper sulfide is not sufficiently generated. As the sulfide, hydrogen sulfide, hydrosulfide and the like can be used.
銅、コバルトおよびニッケルを含む水溶液中（各金属濃度０.２モル/L、液温２５℃）の硫化物の電位−ｐＨグラフを図２に示す。図示する各金属の線より下側が各金属の硫化物が生成する領域であり、各金属の線より上側が金属イオンで存在する領域である。図示ように、ニッケルおよびコバルトがイオン状態のまま選択的に銅の硫化物を沈澱させるｐＨの範囲は、ｐＨ２以上になると狭くなるので、ｐＨ０〜１の範囲で硫化銅を沈澱させるのが好ましい。 FIG. 2 shows a potential-pH graph of sulfide in an aqueous solution containing copper, cobalt, and nickel (each metal concentration 0.2 mol / L, liquid temperature 25 ° C.). The region below each metal line shown in the figure is a region where sulfides of each metal are generated, and the region above each metal line is a region where metal ions are present. As shown in the figure, the pH range in which copper sulfide is selectively precipitated while nickel and cobalt are in an ionic state becomes narrow when the pH is 2 or more. Therefore, it is preferable to precipitate copper sulfide in the pH range of 0-1.
このｐＨ０〜１の範囲において、銅はＨ2Ｓ共存下で酸化還元電位（水素電極基準）０.３９〜０.３４Ｖ以下で硫化物が生成し、一方、コバルトおよびニッケルはそれぞれ酸化還元電位（水素電極基準）が０.１５Ｖ、０.９Ｖで硫化物が生成するため、銅のみを選択的に硫化物として沈殿させるには、酸化還元電位（水素電極基準）を０.３４〜０.１９Ｖにすれば良い。なお、この酸化還元電位はＡｇ/ＡｇＣｌ比較電極では−１５〜１３５ｍＶである。 In this pH range of 0 to 1, sulfides are produced at a redox potential (hydrogen electrode reference) of 0.39 to 0.34 V or less in the presence of H 2 S, while cobalt and nickel are each oxidized at a redox potential ( Since sulfides are generated at 0.15V and 0.9V on the hydrogen electrode standard), in order to precipitate only copper as sulfides, the oxidation-reduction potential (hydrogen electrode standard) is 0.34 to 0.19V. You can do it. This redox potential is −15 to 135 mV for the Ag / AgCl reference electrode.
〔脱アルミニウム工程〕
脱銅溶液にアルカリを添加して水酸化アルミニウムを沈殿させ、該沈殿を固液分離する。上記溶液にアルカリを添加してｐＨ４〜６に調整し、好ましくはｐＨ４.３〜５．０に調整して、水酸化アルミニウムを沈殿させる。溶液のｐＨが４未満では水酸化アルミニウムの生成が不十分になり、ｐＨ６を上回るとコバルトが沈殿し始めるので好ましくない。アルカリとして水酸化ナトリウムやアンモニア水を用いることができる。水酸化アルミニウムの沈殿と共に溶液中のリンおよびフッ素が該水酸化アルミニウム沈殿に取り込まれて共沈する。
[Dealuminization process]
An alkali is added to the copper removal solution to precipitate aluminum hydroxide, and the precipitate is separated into solid and liquid. An alkali is added to the above solution to adjust to pH 4 to 6, preferably pH 4.3 to 5.0, to precipitate aluminum hydroxide. If the pH of the solution is less than 4, the production of aluminum hydroxide becomes insufficient, and if it exceeds pH 6, cobalt begins to precipitate, which is not preferable. Sodium hydroxide or aqueous ammonia can be used as the alkali. Along with precipitation of aluminum hydroxide, phosphorus and fluorine in the solution are taken into the aluminum hydroxide precipitate and coprecipitated.
アルミニウム、コバルト、ニッケルおよびマンガンを含む水溶液において、ｐＨに対する各金属の溶解度の関係を図３に示す。図示するように、アルミニウムはｐＨ３を超えると溶解度が低下して水酸化物の沈殿を生成するようになる。具体的には、アルミニウムの溶解度は、ｐＨ４で１０-2.3モル/L、ｐＨ６では１０-8.3モル/Lである。一方、ニッケル、コバルト、マンガンの溶解度はｐＨ６においても１モル/L程度であり、ｐＨ４〜６においてアルミニウムを選択的に沈殿させることができる。 FIG. 3 shows the relationship of the solubility of each metal with respect to pH in an aqueous solution containing aluminum, cobalt, nickel and manganese. As shown in the figure, when the pH of aluminum exceeds pH 3, the solubility decreases and a precipitate of hydroxide is generated. Specifically, the solubility of aluminum is 10 −2.3 mol / L at pH 4 and 10 −8.3 mol / L at pH 6. On the other hand, the solubility of nickel, cobalt, and manganese is about 1 mol / L even at pH 6, and aluminum can be selectively precipitated at pH 4-6.
〔脱マンガン工程〕
脱アルミニウム溶液に酸化剤を添加してマンガン酸化物を沈殿させ、該沈殿を固液分離する。好ましくは、脱アルミニウム後の溶液を４０℃〜９５℃に加熱し、酸化剤を添加して、酸化還元電位(Ag/AgCl電極基準)９５０〜１０５０ｍＶ、およびｐＨ２.５以下に調整してマンガン酸化物を沈殿させる。酸化剤として次亜塩素酸を用いる場合、ＣｌＯ-/Ｍｎモル比が２.５〜３.５になる量の次亜塩素酸を添加すると良い。
[Demanganese process]
An oxidizing agent is added to the dealumination solution to precipitate manganese oxide, and the precipitate is separated into solid and liquid. Preferably, the dealuminated solution is heated to 40 ° C. to 95 ° C. and an oxidizing agent is added to adjust the oxidation-reduction potential (Ag / AgCl electrode standard) to 950 to 1050 mV and pH 2.5 or less to oxidize manganese. Precipitates. When hypochlorous acid is used as the oxidizing agent, it is preferable to add hypochlorous acid in such an amount that the ClO − / Mn molar ratio is 2.5 to 3.5.
マンガン、コバルトおよびニッケルを含む水溶液中での電位−ｐＨグラフを図４に示す。水溶液のマンガン濃度１モル/L、コバルトとニッケルの各濃度０.２モル/L、液温２５℃であり、図中、実線はマンガン、一点破線はコバルト、二点破線はコバルトである。図示するように、ｐＨ２.５においてマンガンは酸化還元電位（水素電極基準）０.９５Ｖ以上で二酸化マンガンに酸化され沈殿する。一方、ｐＨ２.５においてコバルトおよびニッケルの沈殿が生成する酸化還元電位（水素電極基準）は各々１.３３Ｖ以上、１.３２Ｖ以上である。 FIG. 4 shows a potential-pH graph in an aqueous solution containing manganese, cobalt and nickel. The concentration of manganese in the aqueous solution is 1 mol / L, each concentration of cobalt and nickel is 0.2 mol / L, and the liquid temperature is 25 ° C. In the figure, the solid line is manganese, the dashed line is cobalt, and the dashed line is cobalt. As shown in the figure, at pH 2.5, manganese is oxidized and precipitated into manganese dioxide at an oxidation-reduction potential (hydrogen electrode standard) of 0.95 V or higher. On the other hand, the oxidation-reduction potential (hydrogen electrode reference) at which precipitation of cobalt and nickel is generated at pH 2.5 is 1.33 V or more and 1.32 V or more, respectively.
図４に示すように、マンガン、コバルトおよびニッケルを含む水溶液のｐＨを２.５以下にし、酸化還元電位（水素電極基準）を０.９５〜１.３３Ｖの範囲に調整すれば、マンガンを選択的に沈殿させることができる。なお、この酸化還元電位はＡｇ/ＡｇＣｌ比較電極では７４４〜１１１４ｍＶであるが、低電位側ではマンガンの沈殿率が低く、また、高電位側ではコバルトの沈殿率が大きくなるので、９５０〜１０５０ｍＶに調整するのが好ましい。 As shown in FIG. 4, if the pH of the aqueous solution containing manganese, cobalt and nickel is adjusted to 2.5 or lower and the redox potential (hydrogen electrode standard) is adjusted to the range of 0.95 to 1.33 V, manganese is selected. Can be precipitated. The oxidation-reduction potential is 744 to 1114 mV for the Ag / AgCl reference electrode, but the manganese precipitation rate is low on the low potential side and the cobalt precipitation rate is high on the high potential side. It is preferable to adjust.
以上のように溶液のｐＨが２.５を上回るとマンガンと共にコバルトが沈殿するので好ましくない。また、溶液の酸化還元電位(Ag/AgCl電極基準)が１０５０ｍＶを超えると、あるいは酸化剤として次亜塩素酸を用いたときにＣｌＯ-/Ｍｎモル比が３.５を超えると、コバルトの沈殿量が増加するので好ましくない。また、上記溶液の酸化還元電位(Ag/AgCl電極基準)が９５０ｍＶ未満では、あるいはＣｌＯ-/Ｍｎモル比が２.５未満ではマンガンの沈殿生成が不十分になるので好ましくない。 As described above, if the pH of the solution exceeds 2.5, cobalt is precipitated together with manganese, which is not preferable. Further, when the oxidation-reduction potential (Ag / AgCl electrode standard) of the solution exceeds 1050 mV, or when the ClO − / Mn molar ratio exceeds 3.5 when hypochlorous acid is used as the oxidizing agent, cobalt precipitation occurs. Since the amount increases, it is not preferable. Further, if the oxidation-reduction potential (Ag / AgCl electrode standard) of the above solution is less than 950 mV, or if the ClO − / Mn molar ratio is less than 2.5, manganese precipitates are insufficient, which is not preferable.
〔コバルト、ニッケル回収工程〕
脱マンガン後の溶液からリン酸系酸性抽出溶媒を用いてコバルトおよびニッケルを溶媒抽出して回収することができる。例えば、リン酸系酸性抽出溶媒として、２−エチルヘキシルホスホン酸モノ２−エチルヘキシルエステル（商品名：ＰＣ−８８Ａ）を用い、ミキサーセトラ等の連続式抽出装置によって脱マンガン後の溶液を上記溶媒と接触させてコバルトおよびニッケルをｐＨ４.５〜８の範囲で抽出する。
[Cobalt and nickel recovery process]
Cobalt and nickel can be recovered by solvent extraction from the solution after demanganese using a phosphoric acid-based acidic extraction solvent. For example, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (trade name: PC-88A) is used as a phosphoric acid-based acidic extraction solvent, and the solution after demanganese is brought into contact with the above solvent by a continuous extraction device such as a mixer setra. To extract cobalt and nickel in the pH range of 4.5-8.
抽出に際しては抽出溶媒（ＰＣ−８８Ａ）から水素イオンが放出されるので、中和のために水酸化ナトリウム水溶液、あるいは、アンモニア水等のアルカリを添加しｐＨを調整する。コバルトおよびニッケルを含有した抽出溶媒は、コバルトを含む水溶液（例えば、本ミキサセトラの逆抽出回収液等）と接触させてコバルトとニッケルとを置換（ニッケル洗浄）させニッケルを回収し、コバルトのみを含有する抽出溶媒にした後に、ｐＨ２以下の鉱酸溶液と接触させてコバルトを逆抽出して精製されたコバルト回収液を得ることができる。 Since hydrogen ions are released from the extraction solvent (PC-88A) during extraction, the pH is adjusted by adding an aqueous solution of sodium hydroxide or alkali such as aqueous ammonia for neutralization. The extraction solvent containing cobalt and nickel is brought into contact with an aqueous solution containing cobalt (for example, the back-extracted recovery liquid of this mixer setra) to replace cobalt and nickel (nickel cleaning), recover nickel, and contain only cobalt. After the extraction solvent is used, a cobalt recovery solution purified by back-extracting cobalt by contacting with a mineral acid solution having a pH of 2 or less can be obtained.
本発明の回収方法は、コバルトおよびニッケルと共に銅、アルミニウム、マンガンを含む酸性溶液、例えば、リチウムイオン二次電池の正極活物質を鉱酸で浸出した液から銅、アルミニウム、マンガンが分離されるので、脱マンガン後の溶液から溶媒抽出によってコバルトおよびニッケルを回収する際に、溶媒抽出の負担が少なく、効率よく不純物の少ないコバルトおよびニッケルを回収することができる。 The recovery method of the present invention separates copper, aluminum, and manganese from an acidic solution containing copper, aluminum, and manganese together with cobalt and nickel, for example, a solution obtained by leaching a positive electrode active material of a lithium ion secondary battery with a mineral acid. When cobalt and nickel are recovered from the solution after demanganese by solvent extraction, the burden of solvent extraction is small, and cobalt and nickel with few impurities can be efficiently recovered.
脱銅工程において、溶液の酸化還元電位(Ag/AgCl電極基準)を−１５〜１３５ｍＶ、ｐＨを０〜１に調整することによってコバルトおよびニッケル硫化物の沈殿生成を抑止し、銅を選択的に効率よく沈殿させることができる。また、脱アルミニウム工程において、溶液のｐＨを４〜６に調整することによってコバルトおよびニッケルの沈殿生成を抑制し、アルミニウムを選択的に効率よく沈殿させることができる。さらに、脱マンガン工程において、溶液の酸化還元電位(Ag/AgCl電極基準)を９５０〜１０５０ｍＶ、ｐＨを２.５以下に調整することによってコバルトの沈殿生成を抑制し、マンガンを選択的に効率よく沈殿させることができる。 In the copper removal process, by adjusting the oxidation-reduction potential (Ag / AgCl electrode standard) of the solution to -15 to 135 mV and the pH to 0 to 1, precipitation of cobalt and nickel sulfide is suppressed, and copper is selectively used. It can be precipitated efficiently. Moreover, in the dealumination step, the precipitation of cobalt and nickel can be suppressed by adjusting the pH of the solution to 4 to 6, and aluminum can be selectively and efficiently precipitated. Furthermore, in the demanganese process, by adjusting the oxidation-reduction potential (Ag / AgCl electrode standard) of the solution to 950 to 1050 mV and the pH to 2.5 or less, the precipitation of cobalt is suppressed and manganese is selectively and efficiently produced. Can be precipitated.
本発明の回収方法は、脱銅処理を最初に行うので浸出液のｐＨを大幅に調整せずに硫化物を加えればよく、また脱マンガン処理の後にコバルトおよびニッケルの溶媒抽出を行うので溶液のｐＨを大幅に調整せずに溶媒抽出を行うことができるので、各段階でのｐＨ調整が容易である。 In the recovery method of the present invention, since the copper removal treatment is performed first, it is sufficient to add sulfide without greatly adjusting the pH of the leachate, and since the solvent extraction of cobalt and nickel is performed after the demanganese treatment, the pH of the solution Since the solvent extraction can be carried out without significantly adjusting the pH, pH adjustment at each stage is easy.
本発明の回収方法は、脱アルミニウム工程において、リンとフッ素が水酸化アルミニウムに取り込まれて沈殿するので、脱リンおよび脱フッ素を脱アルミニウムと同時に行うことができる。このため、排水処理の負担が大幅に軽減され、さらにリンやフッ素による汚染が少ないコバルトおよびニッケルを効率よく回収することができる。 In the recovery method of the present invention, phosphorus and fluorine are taken into aluminum hydroxide and precipitated in the dealumination step, so that the phosphorus removal and defluorination can be performed simultaneously with the dealumination. For this reason, the burden of wastewater treatment is greatly reduced, and cobalt and nickel that are less contaminated with phosphorus and fluorine can be efficiently recovered.
以下、本発明の実施例および比較例を示す。
〔実施例１〕
浸出液の調製
使用済みリチウムイオン二次電池を放電後に解体して正極および負極の活物質を選別し、これを６０℃に加熱した１９７ｇ/Lの硫酸１００mlに添加し、１時間撹拌して浸出した。浸出後のｐＨは０であった。浸出後、固液分離して濾液（浸出液）を回収した。表１に浸出液の成分組成を示す。
脱銅処理
表１に示す浸出液を６０℃に加熱し撹拌しながら、ＮａＨＳをＯＲＰ(Ag/AgCl電極基準)で４７ｍＶになるまで添加し、１時間反応させて沈殿を生成させた。生成した硫化銅を固液分離し、濾液１２０ｍｌを回収した。脱銅濾液に含まれる成分濃度および除去率を表２に示す。
脱アルミニウム処理
表２の脱銅後の溶液を撹拌し、ＮａＯＨをｐＨ４.３６になるまで添加し、１時間反応させて沈殿を生成させた。生成したアルミニウム沈殿を固液分離し、濾液１３３ｍｌを回収した。脱アルミニウム濾液に含まれる成分濃度および除去率を表３に示す。
脱マンガン処理
表３の脱アルミニウム後の溶液を６０℃に加熱し撹拌しながら、次亜塩素酸ナトリウム溶液をＣｌＯ-/Ｍｎモル比３.０になるように添加し、ｐＨ２に調整し、１時間反応させて沈殿を生成させた。このときのＯＲＰ（Ag/AgCl電極基準）は１０３０ｍＶであった。生成したマンガン酸化物沈殿を固液分離し、濾液２６５ｍｌを回収した。脱マンガン濾液に含まれる成分濃度および除去率を表４に示す。
コバルト、ニッケル回収処理
脱マンガン濾液を、有機溶媒（２０容量％のＰＣ−８８Ａ/ケロシン）を用い、ミキサセトラに入れて、コバルトとニッケルを抽出し回収した。抽出操作は有機相/水相比が１/２になるように有機相と水相（脱マンガン濾液）を供給した。抽出溶媒のＰＣ−８８Ａは抽出時に水素イオンを放出するので、この水素イオンを中和するために抽出残液のｐＨが７になるように供給される有機相にアンモニア水を添加した。
コバルトおよびニッケルを抽出した有機相は、後工程の逆抽出液の一部を洗浄液として供給し、有機相中に含まれるニッケルと水相中のコバルトとを置換し、ニッケルのみを硫酸ニッケル水溶液として回収した。ニッケルが除かれた有機相は、１モル/Ｌの希硫酸と接触させて逆抽出を行い、硫酸コバルト水溶液として回収した。
回収結果を表５に示す。
Examples of the present invention and comparative examples are shown below.
[Example 1]
Preparation of leachate Disassembled used lithium ion secondary battery after discharge to select positive and negative electrode active materials, added to 100 ml of 197 g / L sulfuric acid heated to 60 ° C., and stirred for 1 hour And leached. The pH after leaching was zero. After leaching, the filtrate (leachate) was recovered by solid-liquid separation. Table 1 shows the component composition of the leachate.
Copper removal treatment While heating the leachate shown in Table 1 to 60C and stirring, NaHS was added to 47 mV by ORP (Ag / AgCl electrode standard) and reacted for 1 hour to form a precipitate. . The produced copper sulfide was subjected to solid-liquid separation, and 120 ml of the filtrate was recovered. Table 2 shows the component concentrations and removal rates contained in the copper removal filtrate.
Dealumination treatment The solution after removing copper in Table 2 was stirred, NaOH was added until the pH reached 4.36, and the mixture was reacted for 1 hour to form a precipitate. The produced aluminum precipitate was subjected to solid-liquid separation, and 133 ml of the filtrate was recovered. Table 3 shows the concentration and removal rate of the components contained in the dealuminated filtrate.
Demanganese treatment While the dealuminated solution in Table 3 was heated to 60 ° C. and stirred, a sodium hypochlorite solution was added to a ClO − / Mn molar ratio of 3.0 to adjust to pH 2. Adjusted and reacted for 1 hour to form a precipitate. The ORP (Ag / AgCl electrode reference) at this time was 1030 mV. The produced manganese oxide precipitate was subjected to solid-liquid separation, and 265 ml of the filtrate was recovered. Table 4 shows the component concentrations and removal rates contained in the demanganese filtrate.
Cobalt and nickel recovery treatment The demanganese filtrate was placed in a mixer setra using an organic solvent (20% by volume of PC-88A / kerosene), and cobalt and nickel were extracted and recovered. In the extraction operation, the organic phase and the aqueous phase (demanganese filtrate) were supplied so that the organic phase / aqueous phase ratio was 1/2. Since the extraction solvent PC-88A releases hydrogen ions during extraction, ammonia water was added to the organic phase supplied so that the pH of the extraction residue was 7 in order to neutralize the hydrogen ions.
In the organic phase from which cobalt and nickel have been extracted, a part of the back-extracted liquid in the subsequent process is supplied as a cleaning liquid, replacing nickel contained in the organic phase with cobalt in the aqueous phase, and only nickel is used as a nickel sulfate aqueous solution. It was collected. The organic phase from which nickel was removed was contacted with 1 mol / L dilute sulfuric acid, back-extracted, and recovered as an aqueous cobalt sulfate solution.
The collection results are shown in Table 5.
〔実施例２、比較例１〕
表１に示す浸出液を６０℃に加熱し撹拌しながら、ＮａＨＳをＯＲＰ(Ag/AgCl電極基準)が０ｍＶになるまで添加し（実施例２）、またはＯＲＰ(Ag/AgCl電極基準)が２００ｍＶになるまで添加し、１時間反応させて沈殿を生成させた（比較例１）。生成した沈殿を固液分離して濾液を回収した。該濾液に含まれる成分濃度および除去率を表６に示す。
実施例２では銅が選択的に沈殿するが、比較例１では銅と共にコバルトが沈殿する。
[Example 2, Comparative Example 1]
While heating the leachate shown in Table 1 to 60 ° C. and stirring, add NaHS until ORP (Ag / AgCl electrode standard) reaches 0 mV (Example 2) or ORP (Ag / AgCl electrode standard) to 200 mV Was added and reacted for 1 hour to produce a precipitate (Comparative Example 1). The produced precipitate was separated into solid and liquid, and the filtrate was recovered. Table 6 shows the concentration and removal rate of the components contained in the filtrate.
In Example 2, copper is selectively precipitated, but in Comparative Example 1, cobalt is precipitated together with copper.
〔実施例３：比較例２〕
表１に示す浸出液にＮａＯＨを添加しｐＨ０.９（実施例３）またはｐＨ１.７（比較例２）に調整した後、６０℃に加熱し撹拌しながら、ＮａＨＳをＯＲＰ(Ag/AgCl電極基準)が１００ｍＶになるまで添加し、１時間反応させて沈殿を生成させた。生成した沈殿を固液分離して濾液を回収した。該濾液に含まれる成分濃度および除去率を表７に示す。
実施例２では銅が収率良く沈殿するが、比較例２では原料液中に銅がわずかに残る。
[Example 3: Comparative Example 2]
After adding NaOH to the leachate shown in Table 1 and adjusting to pH 0.9 (Example 3) or pH 1.7 (Comparative Example 2), NaHS was added to ORP (Ag / AgCl electrode standard while heating to 60 ° C. and stirring). ) Was added to 100 mV and reacted for 1 hour to form a precipitate. The produced precipitate was separated into solid and liquid, and the filtrate was recovered. Table 7 shows the concentration and removal rate of the components contained in the filtrate.
In Example 2, copper precipitates with good yield, but in Comparative Example 2, a slight amount of copper remains in the raw material liquid.
〔実施例４、比較例３、４〕
表２の脱銅後の溶液を撹拌し、ＮａＯＨをｐＨ５.０になるまで添加し（実施例４）、またはｐＨ１またはｐＨ７になるまで添加し（比較例３、４）、１時間反応させて沈殿を生成させた。生成した沈殿を固液分離して濾液を回収した。該濾液に含まれる成分濃度を表８に示す。実施例４ではアルミニウムが選択的に沈殿するが、比較例３ではアルミニウムが沈殿せず、比較例４ではアルミニウムと共にコバルトが沈殿する。
[Example 4, Comparative Examples 3 and 4]
Stir the solution after copper removal in Table 2 and add NaOH until pH 5.0 (Example 4), or add until pH 1 or pH 7 (Comparative Examples 3 and 4), react for 1 hour. A precipitate was formed. The produced precipitate was separated into solid and liquid, and the filtrate was recovered. Table 8 shows the component concentrations contained in the filtrate. In Example 4, aluminum is selectively precipitated, but in Comparative Example 3, aluminum is not precipitated, and in Comparative Example 4, cobalt is precipitated together with aluminum.
〔実施例５、比較例５、６〕
表３の脱アルミニウム後の溶液を６０℃に加熱し撹拌しながら、次亜塩素酸ナトリウム溶液をＯＲＰ（Ag/AgCl電極基準）１０２０ｍＶになるまで添加し（実施例５）、またはＯＲＰ（Ag/AgCl電極基準）９２０ｍＶになるまで添加し（比較例５）、ｐＨ２またはｐＨ４に調整して生成した沈殿を固液分離して濾液を回収した。該濾液に含まれる成分濃度を表９に示す。実施例５ではマンガンが選択的に沈殿するが、比較例５、６ではマンガンと共にコバルトが沈殿する。
[Example 5, Comparative Examples 5 and 6]
While the dealuminated solution in Table 3 is heated to 60 ° C. and stirred, a sodium hypochlorite solution is added until ORP (Ag / AgCl electrode standard) reaches 1020 mV (Example 5), or ORP (Ag / AgCl electrode reference) was added until 920 mV (Comparative Example 5), and the precipitate formed after adjusting to pH 2 or pH 4 was separated into solid and liquid, and the filtrate was recovered. Table 9 shows the component concentrations contained in the filtrate. In Example 5, manganese is selectively precipitated, but in Comparative Examples 5 and 6, cobalt is precipitated together with manganese.
Claims (6)
Adds sulfide to an acidic solution containing copper, aluminum and manganese together with cobalt and nickel to precipitate copper sulfide, separates the precipitate, and adds alkali to the solution after removing copper to precipitate aluminum hydroxide. And removing the precipitate, adding an oxidizing agent to the dealuminated solution to precipitate manganese oxide, separating the precipitate, removing the manganese, and recovering cobalt and nickel from the solution after the manganese removal A method for recovering cobalt and nickel, comprising:
The method for recovering cobalt and nickel according to claim 1, wherein the acidic solution containing copper, aluminum, and manganese together with cobalt and nickel is a liquid obtained by leaching a positive electrode active material of a lithium ion secondary battery with a mineral acid.
In the copper removal step, sulfide is added so that the oxidation-reduction potential (Ag / AgCl electrode standard) of the acidic solution is -15 to 135 mV, and copper sulfide is precipitated under a liquidity of pH 0-1. Alternatively, the method for recovering cobalt and nickel according to claim 2.
4. The method according to claim 1, wherein, in the dealumination step, an alkali is added to the solution after copper removal to precipitate aluminum hydroxide under a pH of 4 to 6 and coprecipitate phosphorus and fluorine in the solution. A method for recovering cobalt and nickel as described above.
In the demanganese step, an oxidizing agent is added to the solution after dealumination to precipitate manganese oxide under liquidity at a redox potential (Ag / AgCl electrode standard) of 950 to 1050 mV and a pH of 2.5 or less. The method for recovering cobalt and nickel according to claim 4.
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