JP5902601B2 - Method for separating metal in mixed metal solution - Google Patents
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- JP5902601B2 JP5902601B2 JP2012272172A JP2012272172A JP5902601B2 JP 5902601 B2 JP5902601 B2 JP 5902601B2 JP 2012272172 A JP2012272172 A JP 2012272172A JP 2012272172 A JP2012272172 A JP 2012272172A JP 5902601 B2 JP5902601 B2 JP 5902601B2
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- 229910052751 metal Inorganic materials 0.000 title claims description 136
- 239000002184 metal Substances 0.000 title claims description 136
- 238000000034 method Methods 0.000 title claims description 38
- 238000000605 extraction Methods 0.000 claims description 96
- 239000000243 solution Substances 0.000 claims description 65
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 61
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 45
- 239000007864 aqueous solution Substances 0.000 claims description 34
- 229910052742 iron Inorganic materials 0.000 claims description 31
- 239000012074 organic phase Substances 0.000 claims description 29
- 239000010949 copper Substances 0.000 claims description 27
- 229910052782 aluminium Inorganic materials 0.000 claims description 26
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 26
- 238000002386 leaching Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- 229910052802 copper Inorganic materials 0.000 claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 20
- 229910052791 calcium Inorganic materials 0.000 claims description 19
- 239000011575 calcium Substances 0.000 claims description 19
- 239000011701 zinc Substances 0.000 claims description 19
- 229910052725 zinc Inorganic materials 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 230000002378 acidificating effect Effects 0.000 claims description 18
- 229910017052 cobalt Inorganic materials 0.000 claims description 17
- 239000010941 cobalt Substances 0.000 claims description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 17
- 230000002000 scavenging effect Effects 0.000 claims description 17
- 238000000638 solvent extraction Methods 0.000 claims description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims description 15
- 229910052744 lithium Chemical group 0.000 claims description 14
- 239000000284 extract Substances 0.000 claims description 13
- 239000007774 positive electrode material Substances 0.000 claims description 13
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 150000002739 metals Chemical class 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 5
- 150000002923 oximes Chemical class 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 239000011734 sodium Substances 0.000 description 30
- 239000008346 aqueous phase Substances 0.000 description 29
- 238000009826 distribution Methods 0.000 description 17
- 235000011121 sodium hydroxide Nutrition 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- 239000011572 manganese Substances 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 238000006386 neutralization reaction Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- MJUVQSGLWOGIOB-UHFFFAOYSA-N 2-[(Z)-hydroxyiminomethyl]-4-nonylphenol Chemical compound OC1=C(C=N/O)C=C(C=C1)CCCCCCCCC MJUVQSGLWOGIOB-UHFFFAOYSA-N 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 238000010979 pH adjustment Methods 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- -1 phosphate ester Chemical class 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005363 electrowinning Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- UWGTVLYQSJNUFP-SILNSSARSA-N 4-dodecyl-2-[(Z)-hydroxyiminomethyl]phenol Chemical compound [H]\C(=N\O)C1=C(O)C=CC(CCCCCCCCCCCC)=C1 UWGTVLYQSJNUFP-SILNSSARSA-N 0.000 description 1
- UHSURKDCQCGNGM-UHFFFAOYSA-N 5-(2-hydroxyimino-2-phenylethyl)nonan-2-ol Chemical compound CCCCC(CCC(C)O)CC(=NO)C1=CC=CC=C1 UHSURKDCQCGNGM-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Secondary Cells (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
本発明は、金属混合溶液中の金属の分離方法に関する。とりわけ、本発明はリチウムイオン電池の正極活物質を含む廃材を酸浸出することによって得られた金属混合溶液から銅、亜鉛、マンガン、カルシウム、アルミニウム及び鉄を分離する方法に関する。 The present invention relates to a method for separating a metal in a metal mixed solution. In particular, the present invention relates to a method for separating copper, zinc, manganese, calcium, aluminum, and iron from a metal mixed solution obtained by acid leaching of a waste material containing a positive electrode active material of a lithium ion battery.
リチウムイオン電池はハイブリッド自動車用として急速に用途が広がっている。更にはユニットの高容量化により大型電池の生産量が急増することが予想される。また、リチウムイオン電池の需要拡大に伴い、リチウムイオン電池からの有価金属回収方法の確立が求められている。 Lithium ion batteries are rapidly expanding their applications for hybrid vehicles. Furthermore, the production volume of large batteries is expected to increase rapidly as the capacity of the unit increases. Further, with the growing demand for lithium ion batteries, establishment of a method for recovering valuable metals from lithium ion batteries is required.
リチウムイオン電池は、主に正極、負極、セパレーター、筐体からなっており、正極はアルミニウム箔等の集電体上にマンガン、コバルト、ニッケル及びリチウム等を含む正極活物質がフッ素系等のバインダーを介して接着した構造となっている。 Lithium ion batteries mainly consist of a positive electrode, a negative electrode, a separator, and a casing, and the positive electrode is a positive electrode active material containing manganese, cobalt, nickel, lithium, etc. on a current collector such as an aluminum foil. It has a structure bonded via.
リチウムイオン電池のリサイクル方法としては、使用済みリチウムイオン電池を焼却、破砕して選別した後の原料を用いて酸浸出を行った後、得られた浸出液から溶媒抽出によってそれぞれの金属を抽出分離する方法が提案されている。しかしながら、原料中に不純物として銅、亜鉛、カルシウム、アルミニウム及び鉄が含まれていると、酸浸出によって銅、亜鉛、カルシウム、アルミニウム及び鉄が浸出され、目的回収物であるコバルト、ニッケル及びリチウムの品質を低下させる。そのため、原料を酸浸出した浸出液中に銅、亜鉛、カルシウム、アルミニウム及び鉄が含まれている場合は、銅、亜鉛、カルシウム、アルミニウム及び鉄の除去が必要となっていた。 As a recycling method for lithium ion batteries, acid leaching is performed using raw materials after incineration, crushing and sorting used lithium ion batteries, and then each metal is extracted and separated by solvent extraction from the obtained leachate. A method has been proposed. However, if copper, zinc, calcium, aluminum, and iron are contained as impurities in the raw material, copper, zinc, calcium, aluminum, and iron are leached by acid leaching, and cobalt, nickel, and lithium, which are target recoveries, are leached. Reduce quality. Therefore, when copper, zinc, calcium, aluminum, and iron are contained in the leachate obtained by acid leaching of the raw material, it is necessary to remove copper, zinc, calcium, aluminum, and iron.
例えば、特開２０１０−１８０４３９号公報（特許文献１）では、中和処理によって鉄及びアルミニウムを除去する方法が記載されている。具体的には、ニッケル及びコバルトと鉄、アルミニウム及びマンガンその他の不純物元素とを含有する硫酸酸性水溶液から、ニッケルを回収する方法であって、下記の工程（１）〜（５）を含むことを特徴とする硫酸酸性水溶液からのニッケル回収方法が開示されている。
工程（１）：前記硫酸酸性水溶液に、亜硫酸ガスと空気又は酸素ガスからなる混合ガスを吹き込みながら、炭酸カルシウムを添加して酸化中和処理に付し、生成された鉄及びアルミニウムを含有する沈殿物（ａ）を除去する。
工程（２）：前記工程（１）で得られた酸化中和処理後液に、水酸化カルシウムを添加して中和処理に付し、ニッケル及びコバルトを含有する混合水酸化物を分離回収する。
工程（３）：前記工程（２）で得られた混合水酸化物を、濃度５０質量％以上の硫酸溶液中で溶解処理に付し、生成されたマンガン及び石膏を含有する沈殿物（ｂ）を除去してニッケル及びコバルトの濃縮液を得る。
工程（４）：前記工程（３）で得られた濃縮液を、燐酸エステル系酸性抽出剤を用いて溶媒抽出処理に付し、ニッケルを含有する抽出残液とコバルトを含有する逆抽出液を得る。
工程（５）：前記工程（４）で得られた抽出残液に、中和剤を添加して中和処理に付し、生成された水酸化ニッケルを分離回収する。
For example, JP 2010-180439 A (Patent Document 1) describes a method of removing iron and aluminum by neutralization treatment. Specifically, it is a method for recovering nickel from a sulfuric acid aqueous solution containing nickel and cobalt and iron, aluminum, manganese and other impurity elements, and includes the following steps (1) to (5). A characteristic nickel recovery method from sulfuric acid aqueous solution is disclosed.
Process (1): Precipitation containing iron and aluminum produced by adding calcium carbonate to the acidic aqueous sulfuric acid solution while blowing a mixed gas composed of sulfurous acid gas and air or oxygen gas, and subjecting to oxidation neutralization treatment. Product (a) is removed.
Step (2): Calcium hydroxide is added to the post-oxidation neutralized solution obtained in the above step (1) and subjected to neutralization to separate and recover the mixed hydroxide containing nickel and cobalt. .
Step (3): The mixed hydroxide obtained in the step (2) is subjected to a dissolution treatment in a sulfuric acid solution having a concentration of 50% by mass or more, and a precipitate (b) containing manganese and gypsum produced. Is removed to obtain a nickel and cobalt concentrate.
Step (4): The concentrated solution obtained in the step (3) is subjected to solvent extraction using a phosphoric acid ester-based acidic extractant, and an extraction residual solution containing nickel and a back extract containing cobalt are obtained. obtain.
Step (5): A neutralizing agent is added to the extraction residual liquid obtained in the step (4) and subjected to neutralization treatment, and the produced nickel hydroxide is separated and recovered.
しかしながら、特開２０１０−１８０４３９号公報（特許文献１）の方法のように中和処理によって鉄及びアルミニウムを除去する方法だと、コバルト及びニッケルが中和時に共沈してロスする割合が高いという問題がある。また、中和処理によって生成した水酸化アルミニウム、水酸化鉄、水酸化コバルト及び水酸化ニッケルは濾過性が悪く、固液分離に非常に時間を有するために、この工程に合わせて他の処理工程全体の処理速度を遅く調整する必要がある。 However, when the method of removing iron and aluminum by neutralization treatment as in the method of Japanese Patent Application Laid-Open No. 2010-180439 (Patent Document 1), the ratio of cobalt and nickel co-precipitated and lost during neutralization is high. There's a problem. In addition, aluminum hydroxide, iron hydroxide, cobalt hydroxide and nickel hydroxide produced by the neutralization treatment have poor filterability and have a very long time for solid-liquid separation. It is necessary to adjust the overall processing speed slowly.
そこで、本発明は、コバルト、ニッケル及びリチウムの少なくとも１種からなる金属群Ａと、銅、亜鉛、マンガン、カルシウム、アルミニウム及び鉄の少なくとも１種からなる金属群Ｂとを含有する金属混合水溶液から効率的に金属群Ｂを分離する方法を提供することを課題とする。 Then, this invention is from the metal mixed aqueous solution containing the metal group A which consists of at least 1 sort (s) of cobalt, nickel, and lithium and the metal group B which consists of at least 1 sort (s) of copper, zinc, manganese, calcium, aluminum, and iron. It is an object of the present invention to provide a method for efficiently separating the metal group B.
本発明者は、上記課題を解決するために鋭意検討した結果、特定の抽出剤を組み合わせて溶媒抽出すると、極めて効率的に銅、亜鉛、マンガン、カルシウム、アルミニウム及び鉄の分離が可能になることを見出した。 As a result of intensive studies to solve the above-mentioned problems, the present inventor can separate copper, zinc, manganese, calcium, aluminum, and iron very efficiently when solvent extraction is performed in combination with a specific extractant. I found.
以上の知見を基礎として完成した本発明は一側面において、
コバルト、ニッケル及びリチウムの少なくとも１種からなる金属群Ａと、銅、亜鉛、マンガン、カルシウム、アルミニウム及び鉄の少なくとも１種からなる金属群Ｂとを含有する金属混合水溶液に対して、燐酸エステル系抽出剤（以下、「第一抽出剤」という。）とオキシム系抽出剤（以下、「第二抽出剤」という。）とを含有する混合抽出剤を使用して溶媒抽出し、当該金属混合溶液から金属群Ｂを分離することを含む金属混合溶液中の金属の分離方法である。
The present invention completed on the basis of the above knowledge, in one aspect,
Phosphoric acid ester system for a mixed metal aqueous solution containing a metal group A consisting of at least one of cobalt, nickel and lithium and a metal group B consisting of at least one of copper, zinc, manganese, calcium, aluminum and iron Solvent extraction is performed using a mixed extractant containing an extractant (hereinafter referred to as “first extractant”) and an oxime-based extractant (hereinafter referred to as “second extractant”), and the metal mixed solution. This is a method for separating a metal in a metal mixed solution, including separating the metal group B from the metal.
本発明に係る金属混合溶液中の金属の分離方法の一実施形態においては、第一抽出剤及び第二抽出剤の体積比は、第一抽出剤：第二抽出剤＝１：１〜５０：１である。 In one embodiment of the method for separating a metal in a mixed metal solution according to the present invention, the volume ratio of the first extractant and the second extractant is such that the first extractant: second extractant = 1: 1 to 50: 1.
本発明に係る金属混合溶液中の金属の分離方法の別の一実施形態においては、金属混合水溶液のｐＨが１．５〜４．５である。 In another embodiment of the method for separating a metal in a metal mixed solution according to the present invention, the pH of the metal mixed aqueous solution is 1.5 to 4.5.
本発明に係る金属混合溶液中の金属の分離方法の更に別の一実施形態においては、第一抽出剤がジ−２−エチルヘキシルリン酸であり、第二抽出剤がアドキシム系抽出剤である。 In still another embodiment of the method for separating a metal in a metal mixed solution according to the present invention, the first extractant is di-2-ethylhexyl phosphoric acid, and the second extractant is an adoxime extractant.
本発明に係る金属混合溶液中の金属の分離方法の更に別の一実施形態においては、混合抽出剤中の第一抽出剤及び第二抽出剤の合計濃度は１０〜３０体積％である。 In still another embodiment of the method for separating a metal in a metal mixed solution according to the present invention, the total concentration of the first extractant and the second extractant in the mixed extractant is 10 to 30% by volume.
本発明に係る金属混合溶液中の金属の分離方法の更に別の一実施形態においては、Ｏ／Ａ比が１〜５である。 In still another embodiment of the method for separating a metal in a mixed metal solution according to the present invention, the O / A ratio is 1-5.
本発明に係る金属混合溶液中の金属の分離方法の更に別の一実施形態においては、前記金属混合溶液がリチウムイオン電池の正極活物質を含む廃材を酸浸出して得られた浸出後液である。 In yet another embodiment of the method for separating a metal in a metal mixed solution according to the present invention, the metal mixed solution is a post-leaching solution obtained by acid leaching a waste material containing a positive electrode active material of a lithium ion battery. is there.
本発明に係る金属混合溶液中の金属の分離方法の更に別の一実施形態においては、上記の金属混合溶液中の金属の分離方法を実施することにより得られた抽出剤（有機相）に対して、酸性水溶液を使用して洗浄することにより、当該抽出剤（有機相）から金属群Ａを分離することを含む。 In still another embodiment of the method for separating a metal in a metal mixed solution according to the present invention, the extractant (organic phase) obtained by carrying out the method for separating a metal in the metal mixed solution is used. And separating the metal group A from the extractant (organic phase) by washing with an acidic aqueous solution.
本発明に係る金属混合溶液中の金属の分離方法の更に別の一実施形態においては、洗浄後、洗浄に使用した酸性水溶液よりもｐＨの低い酸性水溶液を使用して逆抽出を実施することにより、洗浄後の抽出剤（有機相）から金属群Ｂを分離することを含む。 In yet another embodiment of the method for separating a metal in a mixed metal solution according to the present invention, after washing, back extraction is performed using an acidic aqueous solution having a pH lower than that of the acidic aqueous solution used for washing. Separating the metal group B from the extractant (organic phase) after washing.
本発明に係る金属混合溶液中の金属の分離方法の更に別の一実施形態においては、逆抽出後、逆抽出に使用した酸性水溶液よりもｐＨの低い酸性水溶液を使用してスカベンジングを実施することにより、逆抽出後の抽出剤（有機相）に残留している金属を分離することを含む。 In yet another embodiment of the method for separating metals in a mixed metal solution according to the present invention, after back extraction, scavenging is performed using an acidic aqueous solution having a lower pH than the acidic aqueous solution used for back extraction. This involves separating the metal remaining in the extractant (organic phase) after back extraction.
本発明によれば、コバルト、ニッケル及びリチウムの少なくとも１種からなる金属群Ａと、銅、亜鉛、マンガン、カルシウム、アルミニウム及び鉄の少なくとも１種からなる金属群Ｂとを含有する金属混合水溶液から効率的に金属群Ｂを分離することができる。 According to the present invention, from a mixed metal aqueous solution containing a metal group A consisting of at least one of cobalt, nickel and lithium and a metal group B consisting of at least one of copper, zinc, manganese, calcium, aluminum and iron. The metal group B can be separated efficiently.
本発明に係る金属混合溶液中の金属の分離方法の一実施形態においては、コバルト、ニッケル及びリチウムの少なくとも１種からなる金属群Ａと、銅、亜鉛、マンガン、カルシウム、アルミニウム及び鉄の少なくとも１種からなる金属群Ｂとを含有する金属混合水溶液に対して、燐酸エステル系抽出剤（以下、「第一抽出剤」という。）とオキシム系抽出剤（以下、「第二抽出剤」という。）とを含有する混合抽出剤を使用して溶媒抽出し、当該金属混合溶液から金属群Ｂを分離することを含む。 In one embodiment of the method for separating a metal in a metal mixed solution according to the present invention, a metal group A consisting of at least one of cobalt, nickel and lithium, and at least one of copper, zinc, manganese, calcium, aluminum and iron. With respect to the metal mixed aqueous solution containing the metal group B consisting of seeds, a phosphate ester-based extractant (hereinafter referred to as “first extractant”) and an oxime-based extractant (hereinafter referred to as “second extractant”). And solvent extraction using a mixed extractant containing, and separating the metal group B from the metal mixed solution.
本発明の処理対象となる金属混合水溶液としては、コバルト、ニッケル及びリチウムの少なくとも１種からなる金属群Ａと、銅、亜鉛、マンガン、カルシウム、アルミニウム及び鉄の少なくとも１種からなる金属群Ｂとを含有する限り特に制限はないが、典型的には、リチウムイオン電池の正極活物質を含む廃材を酸浸出して得られた浸出後液が挙げられる。具体例としては、正極活物質メーカーから出てくる廃正極活物質、電池メーカーから出てくる正極活物質（場合によっては負極活物質及び溶剤（ＰＶＤＦやＮＭＰ）が混練されている）を焼却・乾燥したもの、アルミニウム箔等の集電体にバインダーを介して正極活物質が接着された正極材、正極材から正極活物質を分離したもの、一般に電池滓や電池破砕粉と呼ばれる電池そのものを焼却・破砕・篩別などして正極活物質を分離したようなものを硫酸等で酸浸出して得られた浸出後液である。リチウムイオン電池以外に由来するものとしては、ＣｕとＮｉを含有するメッキスラッジ等が挙げられる。 The mixed metal aqueous solution to be treated of the present invention includes a metal group A composed of at least one of cobalt, nickel and lithium, and a metal group B composed of at least one of copper, zinc, manganese, calcium, aluminum and iron. As long as it contains, there is no particular limitation, but typically, there is a liquid after leaching obtained by acid leaching of a waste material containing a positive electrode active material of a lithium ion battery. Specific examples include incinerating waste positive electrode active materials from positive electrode active material manufacturers and positive electrode active materials from battery manufacturers (in some cases, negative electrode active materials and solvents (PVDF and NMP) are kneaded). Incinerated dry materials, positive electrode materials with positive electrode active material bonded to a current collector such as aluminum foil, binder, separated positive electrode active material from the positive electrode material, and the battery itself, generally called battery cage or battery crushed powder -It is a liquid after leaching obtained by acid leaching with a sulfuric acid or the like from which the positive electrode active material has been separated by crushing or sieving. Examples of those derived from other than lithium ion batteries include plating sludge containing Cu and Ni.
典型的な実施形態においては、浸出後液は酸性である。斯かる浸出後液は、典型的には、０．１〜１００ｇ／Ｌのコバルト、０．１〜１００ｇ／Ｌのニッケル、０．００１〜５０ｇ／Ｌのリチウム、０．００１〜２０ｇ／Ｌの銅、０．００１〜２０ｇ／Ｌの亜鉛、０．１〜１００ｇ／Ｌのマンガン、０．００１〜２０ｇ／Ｌのカルシウム、０．００１〜２０ｇ／Ｌのアルミニウム、０．００１〜２０ｇ／Ｌの鉄を含有する。斯かる浸出後液は、より典型的には、１〜８０ｇ／Ｌのコバルト、１〜８０ｇ／Ｌのニッケル、０．０１〜２０ｇ／Ｌのリチウム、０．０１〜１０ｇ／Ｌの銅、０．０１〜１０ｇ／Ｌの亜鉛、１〜８０ｇ／Ｌのマンガン、０．０１〜１０ｇ／Ｌのカルシウム、０．０１〜１０ｇ／Ｌのアルミニウム、０．０１〜１０ｇ／Ｌの鉄を含有する。 In an exemplary embodiment, the post-leaching solution is acidic. Such post-leaching solution is typically 0.1-100 g / L cobalt, 0.1-100 g / L nickel, 0.001-50 g / L lithium, 0.001-20 g / L. Copper, 0.001-20 g / L zinc, 0.1-100 g / L manganese, 0.001-20 g / L calcium, 0.001-20 g / L aluminum, 0.001-20 g / L Contains iron. Such post-leaching solution is more typically 1-80 g / L cobalt, 1-80 g / L nickel, 0.01-20 g / L lithium, 0.01-10 g / L copper, 0 0.01 to 10 g / L zinc, 1 to 80 g / L manganese, 0.01 to 10 g / L calcium, 0.01 to 10 g / L aluminum, and 0.01 to 10 g / L iron.
鉄の含有量が多い場合は、鉄は溶媒抽出により抽出されやすいものの逆抽出するのに非常に高い酸濃度（低いｐＨ）の酸と接触させる必要があり、２００ｇ／Ｌ程度の酸濃度（ｐＨ−０．６程度）だと溶媒中に残り溶媒中に蓄積していくため、抽出剤を別途抜き出して鉄を除去するための作業が必要となるので、高濃度の鉄は溶媒抽出に不向きである。そこで、溶媒抽出の前に予め脱鉄しておくことが好ましい。脱鉄の方法としては、特に制限はないが、例えば水溶液中の２価の鉄を３価の鉄に酸化しながら水酸化ナトリウム水溶液を添加して中和した後、固液分離する方法がある。鉄の酸化中和処理は、金属混合水溶液を６０〜８０℃（例：７０℃）に加温し、ｐＨ３．５〜４．０に調整しながら空気吹込む方法や、４０〜６０℃（例：５０℃）に加温し、ｐＨ３．５〜４．０に調整しながら過酸化水素等の酸化剤を溶液中に送り込む方法等がある。 When the iron content is high, iron is easily extracted by solvent extraction, but it must be contacted with an acid with a very high acid concentration (low pH) for back extraction, and an acid concentration (pH of about 200 g / L) -0.6), the remaining amount in the solvent accumulates in the solvent. Therefore, it is necessary to extract the extractant separately and remove the iron, so high concentrations of iron are not suitable for solvent extraction. is there. Therefore, it is preferable to remove iron before solvent extraction. There is no particular limitation on the method of iron removal, but for example, there is a method of solid-liquid separation after neutralizing by adding aqueous sodium hydroxide while oxidizing divalent iron in aqueous solution to trivalent iron. . The iron oxidation neutralization treatment is performed by heating the metal mixed aqueous solution to 60 to 80 ° C. (eg, 70 ° C.) and blowing air while adjusting the pH to 3.5 to 4.0, or 40 to 60 ° C. (example) : 50 ° C), and an oxidizing agent such as hydrogen peroxide is fed into the solution while adjusting the pH to 3.5 to 4.0.
金属混合水溶液のｐＨは低すぎると溶媒抽出時のｐＨ調整が困難になる一方で、高すぎるとコバルトやニッケルまで抽出される場合がある。そこで、金属混合水溶液のｐＨは１．５〜４．５に調整することが好ましく、２．５〜４．０に調整することがより好ましい。ｐＨの調整方法は特に制限はなく、公知の任意の方法を使用すれば良いが、例えばアルカリ又は酸を添加することが挙げられる。典型的な浸出後液はｐＨが１．０〜３．０程度と低いことからアルカリを添加することが多いが、その場合は、苛性ソーダやアンモニアのアルカリを使用することが好ましく、苛性ソーダを使用することがより好ましい。 If the pH of the metal mixed aqueous solution is too low, it is difficult to adjust the pH during solvent extraction, while if too high, cobalt and nickel may be extracted. Therefore, the pH of the metal mixed aqueous solution is preferably adjusted to 1.5 to 4.5, more preferably 2.5 to 4.0. The pH adjustment method is not particularly limited, and any known method may be used. For example, an alkali or an acid may be added. Alkaline is often added since a typical leaching solution has a low pH of about 1.0 to 3.0. In that case, it is preferable to use caustic soda or ammonia alkali, and caustic soda is used. It is more preferable.
本発明においては特定の抽出剤を混合して使用することを特徴の一つとしている。第一抽出剤及び第二抽出剤を併用することにより、金属混合水溶液からの金属群Ｂの分離効率が顕著に向上する。 One feature of the present invention is that a specific extractant is mixed and used. By using a 1st extractant and a 2nd extractant together, the separation efficiency of the metal group B from a metal mixed aqueous solution improves notably.
第一抽出剤は燐酸エステル系の抽出剤であり、燐酸エステルとしては限定的ではないがジ−２−エチルヘキシルリン酸（商品名：Ｄ２ＥＨＰＡ又はＤＥＨＰＡ）等が挙げられる。 The first extractant is a phosphate ester type extractant, and examples of the phosphate ester include, but are not limited to, di-2-ethylhexyl phosphate (trade name: D2EHPA or DEHPA).
第二抽出剤はオキシム系抽出剤であり、好ましくはアルドキシムやアルドキシムが主成分のものが挙げられる。具体的には、限定的ではないが、２−ヒドロキシ−５−ノニルアセトフェノンオキシム（商品名：ＬＩＸ８４）、５−ドデシルサリシルアルドオキシム（商品名：ＬＩＸ８６０）、ＬＩＸ８４とＬＩＸ８６０の混合物（商品名：ＬＩＸ９８４）、５−ノニルサリチルアルドキシム（商品名：ＡＣＯＲＧＡ Ｍ５６４０）が挙げられ、その中でも主に価格面の理由により５−ノニルサリチルアルドキシムが好ましい。 The second extractant is an oxime-based extractant, and preferably includes aldoxime and aldoxime as a main component. Specifically, but not limited to, 2-hydroxy-5-nonylacetophenone oxime (trade name: LIX84), 5-dodecyl salicylaldoxime (trade name: LIX860), a mixture of LIX84 and LIX860 (trade name: LIX984), 5-nonylsalicylaldoxime (trade name: ACORGA M5640), among which 5-nonylsalicylaldoxime is preferred mainly due to price reasons.
第一抽出剤及び第二抽出剤の体積比には特に制限はないが、第二抽出剤は本来銅を選択的に抽出する抽出剤であり、第二抽出剤は銅の抽出を促進する役割を担うことと、第二抽出剤の割合が多いと銅を逆抽出するのに多くの酸を必要とする理由により、第一抽出剤に対して第二抽出剤の体積が少ないことが好ましい。例えば、第一抽出剤及び第二抽出剤の体積比は第一抽出剤：第二抽出剤＝１：１〜５０：１とすることが好ましく、５：１〜１５：１とするのがより好ましい。 The volume ratio of the first extractant and the second extractant is not particularly limited, but the second extractant is originally an extractant that selectively extracts copper, and the second extractant plays a role in promoting copper extraction. It is preferable that the volume of the second extractant is small with respect to the first extractant because of the fact that a large amount of the second extractant and a large amount of the second extractant require a large amount of acid to back-extract copper. For example, the volume ratio of the first extractant and the second extractant is preferably 1st extractant: 2nd extractant = 1: 1 to 50: 1, and more preferably 5: 1 to 15: 1. preferable.
抽出剤は典型的には炭化水素系有機溶剤で希釈して使用することができる。有機溶剤としては芳香族系、パラフィン系、ナフテン系等が挙げられる。本発明に係る金属混合溶液の分離方法の一実施形態においては、混合抽出剤中の第一抽出剤及び第二抽出剤の合計濃度が１０〜３０体積％となるように希釈することができ、粘度、分相性、抽出速度、抽出容量の理由により、２０〜２５体積％となるように希釈することが好ましい。 The extractant can typically be used after diluted with a hydrocarbon-based organic solvent. Examples of the organic solvent include aromatic, paraffinic and naphthenic solvents. In one embodiment of the method for separating a metal mixed solution according to the present invention, the mixture can be diluted so that the total concentration of the first extractant and the second extractant in the mixed extractant is 10 to 30% by volume, For reasons of viscosity, phase separation, extraction speed, and extraction volume, it is preferable to dilute to 20 to 25% by volume.
抽出の手順は常法に従えばよい。一例を挙げれば、金属混合水溶液（水相）と前記抽出剤（有機相）を接触させ、典型的にはミキサーでこれらを攪拌混合（例：２００〜５００ｒｐｍで５〜６０分）し、金属群Ｂのイオンを抽出剤と反応させる。抽出は、常温（例：１５〜２５℃）〜６０℃以下で実施し、抽出速度、分相性、有機溶剤の蒸発の理由により３５〜４５℃で実施することが好ましい。抽出時の平衡ｐＨは２．０〜４．０とするのが好ましいが、抽出率やＡｌの水酸化物発生の理由により２．７〜３．０とするのがより好ましい。抽出反応が起きるとｐＨが低下する傾向があるが、抽出時に苛性ソーダ等のアルカリを適宜添加することでｐＨ調整することができる。その後、セトラーにより、混合した有機相と水相を比重差により分離する。溶媒抽出は繰り返し行ってもよく、例えば有機相と水相が向流接触するようにした多段方式とすることもできる。 The extraction procedure may follow a conventional method. For example, the metal mixed aqueous solution (aqueous phase) and the extractant (organic phase) are brought into contact, and these are typically stirred and mixed with a mixer (eg, 200 to 500 rpm for 5 to 60 minutes), and the metal group The ions of B are reacted with the extractant. Extraction is preferably performed at room temperature (eg, 15 to 25 ° C.) to 60 ° C. or less, and is preferably performed at 35 to 45 ° C. for reasons of extraction speed, phase separation, and evaporation of the organic solvent. The equilibrium pH during extraction is preferably 2.0 to 4.0, but more preferably 2.7 to 3.0 for reasons of extraction rate and generation of Al hydroxide. When the extraction reaction occurs, the pH tends to decrease, but the pH can be adjusted by appropriately adding an alkali such as caustic soda during the extraction. Thereafter, the mixed organic phase and aqueous phase are separated by a difference in specific gravity with a settler. The solvent extraction may be repeated, for example, a multi-stage system in which the organic phase and the aqueous phase are in countercurrent contact.
Ｏ／Ａ比（水相に対する油相の体積比）は、抽出したい金属の含有量によるが、ミキサーセトラーでの操業を考慮すると０．１〜１０とするのが好ましく、１〜５がより好ましい。 The O / A ratio (volume ratio of the oil phase to the aqueous phase) depends on the content of the metal to be extracted, but is preferably 0.1 to 10 and more preferably 1 to 5 in consideration of the operation with the mixer settler. .
溶媒抽出後の、金属群Ａ及び金属群Ｂを含有する抽出剤（有機相）に対しては、洗浄を行うことができる。洗浄は逆抽出液や硫酸、塩酸等の酸性水溶液を使用して、ミキサー等で撹拌混合（例：２００〜５００ｒｐｍで５〜６０分）することにより実施することができる。液としては製品品質、設備腐食防止、排水中の塩化物イオン濃度制限の理由により硫酸を使用することが好ましく、高濃度のＭｎ、例えば３０〜６０ｇ／ＬのＭｎを含む硫酸水溶液を洗浄に使えば抽出されやすいＭｎが有機相に抽出され、反対に抽出されにくいＣｏは水相へ移行しやすい。洗浄後液は抽出前液に戻すことができる。洗浄液のｐＨは抽出した金属群Ａを洗浄するという理由により１．０〜２．５に調整することが好ましく、１．５〜２．３に調整することがより好ましい。洗浄は、常温（例：１５〜２５℃）〜６０℃以下で実施することができ、洗浄速度、分相性、有機溶剤の蒸発の理由により３５〜４５℃で実施することが好ましい。洗浄することにより、金属群Ｂは有機相側にできるだけ保持したまま、溶媒抽出時に有機相側に残留した金属群Ａの多くを水相側に移動させることができ、金属群Ａの回収率を上げることができる。 After the solvent extraction, the extractant (organic phase) containing the metal group A and the metal group B can be washed. Washing can be carried out by using an acidic aqueous solution such as a back extract or sulfuric acid or hydrochloric acid and stirring and mixing with a mixer or the like (eg, 5 to 60 minutes at 200 to 500 rpm). As the liquid, it is preferable to use sulfuric acid for the reasons of product quality, prevention of equipment corrosion, and restriction of chloride ion concentration in the waste water. A sulfuric acid aqueous solution containing a high concentration of Mn, for example, 30-60 g / L of Mn can be used for cleaning. In this case, Mn that is easily extracted is extracted into the organic phase, and Co that is difficult to extract is easily transferred to the aqueous phase. The solution after washing can be returned to the solution before extraction. The pH of the cleaning solution is preferably adjusted to 1.0 to 2.5, more preferably 1.5 to 2.3, because the extracted metal group A is cleaned. The washing can be carried out at ordinary temperature (for example, 15 to 25 ° C.) to 60 ° C. or less, and is preferably carried out at 35 to 45 ° C. for reasons of washing speed, phase separation and evaporation of the organic solvent. By washing, the metal group B can be moved to the water phase while most of the metal group A remaining on the organic phase side can be moved while extracting the solvent while keeping the metal group B on the organic phase side as much as possible. Can be raised.
洗浄後の、金属群Ｂを含有する抽出剤（有機相）に対しては、逆抽出を行うことができる。逆抽出は硫酸、塩酸等の酸性水溶液を使用して、ミキサー等で撹拌混合（例：２００〜５００ｒｐｍで５〜６０分）することにより実施することができる。逆抽出液としては製品品質、設備腐食防止、排水中の塩化物イオン濃度制限の理由により硫酸を使用することが好ましい。逆抽出液のｐＨは抽出した金属Ｂを逆抽出することと、後工程に移行する酸の量を少なくする理由により、洗浄に使用する酸性水溶液よりもｐＨを低くし、−０．６〜２．０（硫酸濃度０．５〜２００ｇ／ｌ）に調整することが好ましく、−０．３〜０．３（硫酸濃度２５〜１００ｇ／ｌ）に調整することがより好ましい。逆抽出は、常温（例：１５〜２５℃）〜６０℃以下で実施することができ、逆抽出速度、分相性、有機溶剤の蒸発の理由により３５〜４５℃で実施することが好ましい。逆抽出することにより、金属群Ｂの多くを水相側に移動させることができる。これによって、水相側に移動した金属群Ｂを中和などによって更に処理することができる。 Back extraction can be performed on the extractant (organic phase) containing metal group B after washing. Back extraction can be performed by using an acidic aqueous solution such as sulfuric acid or hydrochloric acid and stirring and mixing with a mixer or the like (eg, 5 to 60 minutes at 200 to 500 rpm). As the back extract, sulfuric acid is preferably used for reasons of product quality, prevention of equipment corrosion, and restriction of chloride ion concentration in the waste water. The pH of the back extract is lower than that of the acidic aqueous solution used for washing due to the back extraction of the extracted metal B and the reduction in the amount of acid transferred to the subsequent step. It is preferable to adjust to 0.0 (sulfuric acid concentration of 0.5 to 200 g / l), and it is more preferable to adjust to -0.3 to 0.3 (sulfuric acid concentration of 25 to 100 g / l). Back extraction can be performed at room temperature (eg, 15 to 25 ° C.) to 60 ° C. or less, and is preferably performed at 35 to 45 ° C. for reasons of back extraction speed, phase separation, and evaporation of the organic solvent. By reverse extraction, most of the metal group B can be moved to the water phase side. Thereby, the metal group B which has moved to the aqueous phase side can be further processed by neutralization or the like.
逆抽出後の抽出剤（有機相）に対しては、抽出剤（有機相）中に残っている金属を除くことを目的としてスカベンジングを実施することができる。スカベンジングは、硫酸、塩酸等の酸性水溶液を使用して、ミキサー等で撹拌混合（例：２００〜５００ｒｐｍで５〜６０分）することにより実施することができる。スカベンジング液としては製品品質、設備腐食防止、排水中の塩化物イオン濃度制限の理由により硫酸を使用することが好ましい。スカベンジング液のｐＨは逆抽出後に抽出剤（有機相）中に残っている金属を可能な限り多く取り除くことと、後工程に移行する酸の量を少なくする理由により逆抽出に使用する酸性水溶液よりもｐＨを低くし、−０．９〜０．３（硫酸濃度２５〜４００ｇ／Ｌ）に調整することが好ましく、−０．７〜−０．３（硫酸濃度１００〜２５０ｇ／Ｌ）に調整することがより好ましい。スカベンジングは、常温（例：１５〜２５℃）〜６０℃以下で実施することができ、スカベンジング速度、分相性、有機溶剤の蒸発の理由により３５〜４５℃で実施することが好ましい。スカベンジングすることにより、金属群Ｂの逆抽出後に抽出剤（有機相）中に残っている金属の多くを水相側に移動させることができる。これによって、抽出剤を再利用することができる。 For the extractant (organic phase) after back extraction, scavenging can be performed for the purpose of removing the metal remaining in the extractant (organic phase). Scavenging can be performed by using an acidic aqueous solution such as sulfuric acid and hydrochloric acid and stirring and mixing with a mixer or the like (eg, 5 to 60 minutes at 200 to 500 rpm). As the scavenging liquid, it is preferable to use sulfuric acid for the reasons of product quality, prevention of equipment corrosion, and restriction of chloride ion concentration in waste water. The pH of the scavenging solution is to remove as much metal as possible in the extractant (organic phase) after back extraction, and to reduce the amount of acid transferred to the post-process, and the acidic aqueous solution used for back extraction It is preferable to adjust the pH to -0.9 to 0.3 (sulfuric acid concentration 25 to 400 g / L), and to -0.7 to -0.3 (sulfuric acid concentration 100 to 250 g / L). It is more preferable to adjust. Scavenging can be carried out at room temperature (for example, 15 to 25 ° C.) to 60 ° C. or less, and is preferably carried out at 35 to 45 ° C. for the reasons of scavenging speed, phase separation, and evaporation of the organic solvent. By scavenging, most of the metal remaining in the extractant (organic phase) after back extraction of the metal group B can be moved to the aqueous phase side. Thereby, the extractant can be reused.
以下、本発明の実施例を説明するが、実施例は例示目的であって発明が限定されることを意図しない。 Examples of the present invention will be described below, but the examples are for illustrative purposes and are not intended to limit the invention.
（実施例１）
リチウムイオン電池の電池破砕粉を硫酸浸出して得られる浸出後液を模した種々の金属を含む抽出前液（ｐＨ：３．８）を用意した。各金属の濃度は表１に示してある。
なお、各金属の濃度はIＣＰにより測定した。
また、ジ−２−エチルヘキシルリン酸（商品名：Ｄ２ＥＨＰＡ）を２３体積％、５−ノニルサリチルアルドキシム（商品名：ＡＣＯＲＧＡ Ｍ５６４０）を２体積％、直鎖系炭化水素が主成分の有機溶剤（商品名：Ｓｈｅｌｌｓｏｌ Ｄ７０）を７５体積％を含有する抽出剤を用意した。
抽出前液と抽出剤をＯ／Ａ比＝３になるように向流多段ミキサーセトラー（抽出段数：３段）を使用して混合撹拌（４００ｒｐｍ）し、溶媒抽出を行った。この際、ミキサーセトラー中にｐＨ調整のための苛性ソーダを添加した。抽出時の平衡ｐＨは２．９であった。各段の抽出段における撹拌時間は１５分とした。抽出時の液温は２５〜３０℃に維持した。抽出後液（水相）中の各元素の濃度及び水相側への分配率を表２に示す。分配率は（抽出後液中の金属量）／（抽出前液中の金属量）の計算式により算出し、Ｎａのみ（抽出後液中のＮａ量）／（抽出前液中のＮａ量＋添加した苛性ソーダのＮａ量）の計算式により算出した。
(Example 1)
Pre-extraction solutions (pH: 3.8) containing various metals simulating post-leaching solutions obtained by leaching the crushed lithium ion battery powder with sulfuric acid were prepared. The concentration of each metal is shown in Table 1.
The concentration of each metal was measured by ICP.
In addition, organic solvent (mainly 23% by volume of di-2-ethylhexyl phosphoric acid (trade name: D2EHPA), 2% by volume of 5-nonylsalicylaldoxime (trade name: ACORGA M5640), and a linear hydrocarbon as a main component ( An extractant containing 75% by volume of trade name: Shellsol D70) was prepared.
The pre-extraction solution and the extraction agent were mixed and stirred (400 rpm) using a countercurrent multi-stage mixer settler (number of extraction stages: 3 stages) so that the O / A ratio = 3, and solvent extraction was performed. At this time, caustic soda for pH adjustment was added to the mixer settler. The equilibrium pH at the time of extraction was 2.9. The stirring time in each extraction stage was 15 minutes. The liquid temperature during extraction was maintained at 25-30 ° C. Table 2 shows the concentration of each element in the liquid after extraction (aqueous phase) and the distribution ratio to the aqueous phase side. The distribution ratio is calculated by the formula of (amount of metal in the solution after extraction) / (amount of metal in the solution before extraction), and only Na (amount of Na in the solution after extraction) / (amount of Na in the solution before extraction + It was calculated by a calculation formula of Na amount of added caustic soda.
上記の結果より、Ｍｎ、Ｆｅ、Ａｌ、Ｃｕ、Ｚｎ及びＣａの大部分は油相側に移行したことが分かる。そして、溶媒抽出後もＣｏ、Ｎｉ及びＬｉはほとんどロスすることなく、水相側に残っていることが分かる。 From the above results, it can be seen that most of Mn, Fe, Al, Cu, Zn and Ca have moved to the oil phase side. And even after solvent extraction, it turns out that Co, Ni, and Li remain on the water phase side with almost no loss.
次に、抽出後の有機相を洗浄液（ｐＨ＝１．７のＭｎ濃度が５１，０００ｍｇ／Ｌの硫酸水溶液）を使用して洗浄した。洗浄は抽出後の有機相と洗浄液をＯ／Ａ比＝１になるように向流多段ミキサーセトラー（洗浄段数：１段）を使用して混合撹拌（４００ｒｐｍ）することにより行った。洗浄段における撹拌時間は２９分とした。洗浄時の液温は２５〜３０℃に維持した。洗浄液（水相）中の各元素の濃度及び水相側への分配率を表３に示す。分配率は（洗浄液中の金属量増加量）／（抽出前液中の金属量）の計算式により算出し、Ｎａのみ（洗浄液中のＮａ量増加量）／（抽出前液中のＮａ量＋添加した苛性ソーダのＮａ量）の計算式により算出した。 Next, the organic phase after extraction was washed using a washing solution (aqueous sulfuric acid solution having a Mn concentration of 51.7 mg / L at pH = 1.7). Washing was performed by mixing and stirring (400 rpm) using a countercurrent multi-stage mixer settler (number of washing stages: 1 stage) so that the organic phase and the washing liquid after extraction were O / A ratio = 1. The stirring time in the washing stage was 29 minutes. The liquid temperature at the time of washing | cleaning was maintained at 25-30 degreeC. Table 3 shows the concentration of each element in the cleaning liquid (aqueous phase) and the distribution ratio to the aqueous phase side. The distribution rate is calculated by the formula of (amount of increase in metal in the washing solution) / (amount of metal in the solution before extraction), and Na alone (increase in the amount of Na in the washing solution) / (amount of Na in the solution before extraction + It was calculated by a calculation formula of Na amount of added caustic soda.
上記の結果より、抽出されたＣｏ，Ｎｉ及びＬｉは洗浄によりほとんどが水相側に移行したことが分かる。洗浄液は抽出前液へ繰り返しとする。 From the above results, it can be seen that most of the extracted Co, Ni and Li moved to the aqueous phase side by washing. Repeat washing to pre-extraction solution.
次に、洗浄後の有機相を硫酸水溶液（Ｈ2ＳＯ4濃度：７５ｇ／Ｌ；ｐＨ＝−０．１８）を逆抽出液として使用して逆抽出した。逆抽出は洗浄後の有機相と逆抽出剤をＯ／Ａ比＝１になるように向流多段ミキサーセトラー（逆抽出段数：１段）を使用して混合撹拌（４００ｒｐｍ）することにより行った。逆抽出段における撹拌時間は２９分とした。抽出時の液温は２５〜３０℃に維持した。逆抽出後液（水相）中の各元素の濃度及び水相側への分配率を表４に示す。分配率は（逆抽出液中の金属量増加量）／（抽出前液中の金属量）の計算式により算出し、Ｎａのみ（逆抽出液中のＮａ量増加量）／（抽出前液中のＮａ量＋添加した苛性ソーダのＮａ量）の計算式により算出した。 Next, the organic phase after washing was back extracted using an aqueous sulfuric acid solution (H 2 SO 4 concentration: 75 g / L; pH = −0.18) as a back extract. Back extraction was performed by mixing and stirring (400 rpm) using a countercurrent multi-stage mixer settler (number of back extraction stages: 1 stage) so that the organic phase and back extractant after washing were O / A ratio = 1. . The stirring time in the back extraction stage was 29 minutes. The liquid temperature during extraction was maintained at 25-30 ° C. Table 4 shows the concentration of each element in the liquid after back extraction (aqueous phase) and the distribution ratio to the aqueous phase side. The distribution rate is calculated by the formula of (amount of increase in metal in the back extract) / (amount of metal in the solution before extraction), and Na alone (increase in the amount of Na in the back extract) / (in the solution before extraction) Na amount + Na amount of added caustic soda).
上記の結果より、Ｍｎ、Ｃｕ、Ａｌ、Ｚｎ及びＣａの多くが水相側に移行したことが分かる。Ｃｏ、Ｎｉ及びＮａが検出されているがほとんどが逆抽出液中にもともと混入されていた分である。 From the above results, it can be seen that most of Mn, Cu, Al, Zn and Ca have moved to the aqueous phase side. Co, Ni and Na are detected, but most of them are originally mixed in the back extract.
逆抽出後の有機相に対しては、再度、硫酸水溶液（Ｈ2ＳＯ4濃度：２００ｇ／Ｌ；ｐＨ＝−０．６１）をスカベンジング液として使用してスカベンジングを実施した。スカベンジングは逆抽出後の有機相とスカベンジング液をＯ／Ａ比＝１になるように向流多段ミキサーセトラー（スカベンジング段数：１段）を使用して混合撹拌（４００ｒｐｍ）することにより行った。スカベンジング段における撹拌時間は２９分とした。抽出時の液温は２５〜３０℃に維持した。スカベンジング液（水相）中の各元素の濃度及び水相側への分配率を表５に示す。分配率は（スカベンジング液中の金属量増加量）／（抽出前液中の金属量）の計算式により算出し、Ｎａのみ（スカベンジング液中のＮａ量増加量）／（抽出前液中のＮａ量＋添加した苛性ソーダのＮａ量）の計算式により算出した。 The organic phase after back extraction was scavenged again using an aqueous sulfuric acid solution (H 2 SO 4 concentration: 200 g / L; pH = −0.61) as the scavenging solution. Scavenging is performed by mixing and stirring (400 rpm) the counter-extracted organic phase and the scavenging liquid using a countercurrent multistage mixer settler (number of scavenging stages: 1 stage) so that the O / A ratio = 1. It was. The stirring time in the scavenging stage was 29 minutes. The liquid temperature during extraction was maintained at 25-30 ° C. Table 5 shows the concentration of each element in the scavenging liquid (aqueous phase) and the distribution ratio to the aqueous phase side. The distribution rate is calculated by the formula (increased amount of metal in scavenging solution) / (amount of metal in solution before extraction), and only Na (increased amount of Na in scavenging solution) / (in solution before extraction) Na amount + Na amount of added caustic soda).
上記の結果より、逆抽出後に抽出剤（有機相）中に残っている金属であるＭｎ、Ｃｕ、Ｆｅ、Ａｌ、Ｚｎ及びＣａのうち、Ｍｎ、Ｃｕ、Ａｌ、Ｚｎ及びＣａのほぼ全量が水相側に移行し、Ｆｅは抽出剤（有機相）中に残ったことが分かる。Ｃｏ、Ｎｉ及びＮａが検出されているがほとんどが逆抽出液中にもともと混入されていた分である。 From the above results, among Mn, Cu, Fe, Al, Zn and Ca, which are metals remaining in the extractant (organic phase) after back extraction, almost all of Mn, Cu, Al, Zn and Ca are water. It moves to the phase side and it turns out that Fe remained in the extractant (organic phase). Co, Ni and Na are detected, but most of them are originally mixed in the back extract.
（比較例１）（Ｄ２ＥＨＰＡのみ）
リチウムイオン電池の電池破砕粉を硫酸浸出して得られる浸出後液を模した種々の金属を含む抽出前液（ｐＨ：４．０）を用意した。各金属の濃度は表６に示してある。
なお、各金属の濃度はIＣＰにより測定した。
また、ジ−２−エチルヘキシルリン酸（商品名：Ｄ２ＥＨＰＡ）を２５体積％、直鎖系炭化水素が主成分の有機溶剤（商品名：Ｓｈｅｌｌｓｏｌ Ｄ７０）を７５体積％を含有する抽出剤を用意した。
抽出前液と抽出剤をＯ／Ａ比＝４になるように向流多段ミキサーセトラー（抽出段数：３段）を使用して混合撹拌（４００ｒｐｍ）し、溶媒抽出を行った。この際、ミキサーセトラー中にｐＨ調整のための苛性ソーダを添加した。抽出時の平衡ｐＨは２．９であった。各段の抽出段における撹拌時間は１５分とした。抽出時の液温は２５〜３０℃に維持した。抽出後液（水相）中の各元素の濃度及び水相側への分配率を表７に示す。分配率は（抽出後液中の金属量）／（抽出前液中の金属量）の計算式により算出し、Ｎａのみ（抽出後液中のＮａ量）／（抽出前液中のＮａ量＋添加した苛性ソーダのＮａ量）の計算式により算出した。
(Comparative Example 1) (D2EHPA only)
Pre-extraction solutions (pH: 4.0) containing various metals simulating the post-leaching solution obtained by leaching the battery crushed powder of a lithium ion battery with sulfuric acid were prepared. The concentration of each metal is shown in Table 6.
The concentration of each metal was measured by ICP.
In addition, an extractant containing 25% by volume of di-2-ethylhexyl phosphoric acid (trade name: D2EHPA) and 75% by volume of an organic solvent mainly composed of linear hydrocarbon (trade name: Shellsol D70) was prepared. .
The pre-extraction solution and the extraction agent were mixed and stirred (400 rpm) using a countercurrent multi-stage mixer settler (extraction stage number: 3 stages) so that the O / A ratio = 4, and solvent extraction was performed. At this time, caustic soda for pH adjustment was added to the mixer settler. The equilibrium pH at the time of extraction was 2.9. The stirring time in each extraction stage was 15 minutes. The liquid temperature during extraction was maintained at 25-30 ° C. Table 7 shows the concentration of each element in the liquid after extraction (aqueous phase) and the distribution ratio to the aqueous phase side. The distribution ratio is calculated by the formula of (amount of metal in the solution after extraction) / (amount of metal in the solution before extraction), and only Na (amount of Na in the solution after extraction) / (amount of Na in the solution before extraction + It was calculated by a calculation formula of Na amount of added caustic soda.
上記の結果より、実施例１に比べて水相に残留したＣｕの量が多いことが分かる。Ｃｕが水相に残留していると、後にＣｏを抽出する際にＣｕも一緒に抽出され、Ｃｏの抽出液からＣｏ電解採取を行う場合であればＣｏ電解採取のときに一緒に電着してしまうという問題が生じる。また、Ｏ／Ａ比が高めであり、実施例１よりもＣｏの水相への分配率が低下した。 From the above results, it can be seen that the amount of Cu remaining in the aqueous phase is larger than that in Example 1. If Cu remains in the aqueous phase, Cu is also extracted when Co is extracted later, and if Co electrowinning is performed from the Co extract, it is electrodeposited together during Co electrowinning. Problem arises. Further, the O / A ratio was high, and the distribution ratio of Co to the aqueous phase was lower than that in Example 1.
（比較例２）（ＡＣＯＲＧＡ Ｍ５６４０のみ）
リチウムイオン電池の電池破砕粉を硫酸浸出して得られる浸出後液を模した種々の金属を含む抽出前液（ｐＨ：３．５）を用意した。各金属の濃度は表８に示してある。
なお、各金属の濃度はＩＣＰにより測定した。
また、５−ノニルサリチルアルドキシム（商品名：ＡＣＯＲＧＡ Ｍ５６４０）を２５体積％、直鎖系炭化水素が主成分の有機溶剤（商品名：Ｓｈｅｌｌｓｏｌ Ｄ７０）を７５体積％を含有する抽出剤を用意した。
抽出前液と抽出剤をＯ／Ａ比＝１になるように向流多段ミキサーセトラー（抽出段数：３段）を使用して混合撹拌（４００ｒｐｍ）し、溶媒抽出を行った。この際、ミキサーセトラー中にｐＨ調整のための苛性ソーダを添加した。抽出時の平衡ｐＨは２．８であった。各段の抽出段における撹拌時間は１５分とした。抽出時の液温は２５〜３０℃に維持した。抽出後液（水相）中の各元素の濃度及び水相側への分配率を表９に示す。分配率は（抽出後液中の金属量）／（抽出前液中の金属量）の計算式により算出し、Ｎａのみ（抽出後液中のＮａ量）／（抽出前液中のＮａ量＋添加した苛性ソーダのＮａ量）の計算式により算出した。
(Comparative Example 2) (ACORGA M5640 only)
Pre-extraction solutions (pH: 3.5) containing various metals simulating the post-leaching solution obtained by leaching the battery crushed powder of a lithium ion battery with sulfuric acid were prepared. The concentration of each metal is shown in Table 8.
The concentration of each metal was measured by ICP.
Further, an extractant containing 25% by volume of 5-nonylsalicylaldoxime (trade name: ACORGA M5640) and 75% by volume of an organic solvent (trade name: Shellsol D70) mainly composed of linear hydrocarbons was prepared. .
The pre-extraction solution and the extractant were mixed and stirred (400 rpm) using a countercurrent multi-stage mixer settler (extraction stage number: 3 stages) so that the O / A ratio = 1, and solvent extraction was performed. At this time, caustic soda for pH adjustment was added to the mixer settler. The equilibrium pH at the time of extraction was 2.8. The stirring time in each extraction stage was 15 minutes. The liquid temperature during extraction was maintained at 25-30 ° C. Table 9 shows the concentration of each element in the liquid after extraction (aqueous phase) and the distribution ratio to the aqueous phase side. The distribution ratio is calculated by the formula of (amount of metal in the solution after extraction) / (amount of metal in the solution before extraction), and only Na (amount of Na in the solution after extraction) / (amount of Na in the solution before extraction + It was calculated by a calculation formula of Na amount of added caustic soda.
上記の結果より、Ｃｕ以外はほとんど抽出されずに水相に残留したことが分かる。 From the above results, it can be seen that except Cu was hardly extracted and remained in the aqueous phase.
（実施例２）
リチウムイオン電池の電池破砕粉を硫酸浸出して得られる浸出後液を模した種々の金属を含む抽出前液（ｐＨ：３．８）を用意した。各金属の濃度は表１０に示してある。
なお、各金属の濃度はIＣＰにより測定した。
また、ジ−２−エチルヘキシルリン酸（商品名：Ｄ２ＥＨＰＡ）を２０体積％、５−ノニルサリチルアルドキシム（商品名：ＡＣＯＲＧＡ Ｍ５６４０）を５体積％、直鎖系炭化水素が主成分の有機溶剤（商品名：Ｓｈｅｌｌｓｏｌ Ｄ７０）を７５体積％を含有する抽出剤を用意した。
抽出前液と抽出剤をＯ／Ａ比＝４になるように向流多段ミキサーセトラー（抽出段数：３段）を使用して混合撹拌（４００ｒｐｍ）し、溶媒抽出を行った。この際、ミキサーセトラー中にｐＨ調整のための苛性ソーダを添加した。抽出時の平衡ｐＨは３．２であった。各段の抽出段における撹拌時間は１５分とした。抽出時の液温は２５〜３０℃に維持した。抽出後液（水相）中の各元素の濃度及び水相側への分配率を表１１に示す。分配率は（抽出後液中の金属量）／（抽出前液中の金属量）の計算式により算出し、Ｎａのみ（抽出後液中のＮａ量）／（抽出前液中のＮａ量＋添加した苛性ソーダのＮａ量）の計算式により算出した。
(Example 2)
Pre-extraction solutions (pH: 3.8) containing various metals simulating post-leaching solutions obtained by leaching the crushed lithium ion battery powder with sulfuric acid were prepared. The concentration of each metal is shown in Table 10.
The concentration of each metal was measured by ICP.
In addition, 20% by volume of di-2-ethylhexyl phosphoric acid (trade name: D2EHPA), 5% by volume of 5-nonylsalicylaldoxime (trade name: ACORGA M5640), and an organic solvent mainly composed of a linear hydrocarbon ( An extractant containing 75% by volume of trade name: Shellsol D70) was prepared.
The pre-extraction solution and the extraction agent were mixed and stirred (400 rpm) using a countercurrent multi-stage mixer settler (extraction stage number: 3 stages) so that the O / A ratio = 4, and solvent extraction was performed. At this time, caustic soda for pH adjustment was added to the mixer settler. The equilibrium pH at the time of extraction was 3.2. The stirring time in each extraction stage was 15 minutes. The liquid temperature during extraction was maintained at 25-30 ° C. Table 11 shows the concentration of each element in the liquid after extraction (aqueous phase) and the distribution ratio to the aqueous phase side. The distribution ratio is calculated by the formula of (amount of metal in the solution after extraction) / (amount of metal in the solution before extraction), and only Na (amount of Na in the solution after extraction) / (amount of Na in the solution before extraction + It was calculated by a calculation formula of Na amount of added caustic soda.
実施例１に比べてＣｏ、Ｎｉ及びＬｉの水相への分配率が低かったことが分かる。これは、Ｏ／Ａ比が高めであり、実施例１よりもＣｏ、Ｎｉの水相への分配率が低下した。また、ｐＨが実施例１に比べて高く、Ａｌの水酸化物が２５％分発生した。このため実際には、抽出７４％＋水酸化物として沈殿２５％＋未抽出０．６％＝１００％（トータル）であった。 Compared to Example 1, it can be seen that the distribution ratio of Co, Ni, and Li to the aqueous phase was low. This is because the O / A ratio is high, and the distribution ratio of Co and Ni to the aqueous phase is lower than in Example 1. Further, the pH was higher than that of Example 1, and 25% of Al hydroxide was generated. Therefore, in practice, it was 74% extracted + 25% precipitate as hydroxide + 0.6% unextracted = 100% (total).
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