JP2012211386A - Method for extracting aluminum with solvent - Google Patents
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- JP2012211386A JP2012211386A JP2012032597A JP2012032597A JP2012211386A JP 2012211386 A JP2012211386 A JP 2012211386A JP 2012032597 A JP2012032597 A JP 2012032597A JP 2012032597 A JP2012032597 A JP 2012032597A JP 2012211386 A JP2012211386 A JP 2012211386A
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 85
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000002904 solvent Substances 0.000 title abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000605 extraction Methods 0.000 claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 16
- 238000004064 recycling Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 238000000638 solvent extraction Methods 0.000 claims description 19
- 239000003929 acidic solution Substances 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 17
- 150000002739 metals Chemical class 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002994 raw material Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- -1 phosphate ester Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
Description
本発明は、アルミニウムの溶媒抽出方法に関する。 The present invention relates to a solvent extraction method for aluminum.
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おり、更にユニットの高容量化により大型のもの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対して、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。 The use of lithium ion batteries is rapidly expanding for hybrid vehicles, and the production volume of large-sized batteries is expected to increase rapidly as the capacity of the units increases. Moreover, establishment of the valuable metal recovery method from a lithium ion battery is calculated | required with respect to the demand expansion of a lithium ion battery.
この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の集電体上にマンガン、コバルト、ニッケル、リチウムを含む正極活物質とカーボンブラック等の導電剤をフッ素系等のバインダーに混練、塗布した構造となっている。正極材は厚み１５ミクロン程度のアルミニウム箔と正極活物質を含むバインダー層からなっており、外観はアルミニウム箔上に黒色の正極活物質が塗布されている。 This lithium ion battery mainly consists of a positive electrode, a negative electrode, a separator, and a casing. The positive electrode has a positive electrode active material containing manganese, cobalt, nickel, lithium and a conductive agent such as carbon black on an aluminum foil current collector. The structure is kneaded and applied to a fluorine-based binder. The positive electrode material is composed of an aluminum foil having a thickness of about 15 microns and a binder layer containing a positive electrode active material, and a black positive electrode active material is coated on the aluminum foil.
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、選別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、原料中に不純物として正極材のアルミニウムが含まれていると、酸浸出によってアルミニウムが浸出され、溶媒抽出における抽出分離に悪影響が出る。そのため、原料を酸浸出した浸出液中にアルミニウムが含まれている場合は、アルミニウムの除去が必要となっている。 As a method for recycling lithium ion batteries, used lithium ion batteries are incinerated and crushed, and after acid leaching using the selected raw materials, each metal is extracted and separated by solvent extraction from the obtained leachate Has been proposed. However, if the positive electrode aluminum is contained as an impurity in the raw material, the aluminum is leached by acid leaching, which adversely affects the extraction and separation in the solvent extraction. Therefore, when aluminum is contained in the leachate obtained by acid leaching of the raw material, it is necessary to remove the aluminum.
酸性溶液中のアルミニウムの除去方法としては、中和法や硫酸アルミニウム法、溶媒抽出法などが提案されている。中和法としては、特許文献１（特開２００４−３３９８４号公報）に開示されているように、水酸化ナトリウムなどの中和剤を添加し、ｐＨを６〜８の範囲に中和する方法が提案されている。また、硫酸アルミニウム法としては、特許文献２（特開平１−１５３５１７号公報）に記載されているように、ＳＯ4／Ａｌモル比を３／２〜９／２として、減圧濃縮、冷却を行って硫酸アルミニウムを析出させる方法が提案されている。 As a method for removing aluminum in an acidic solution, a neutralization method, an aluminum sulfate method, a solvent extraction method, and the like have been proposed. As a neutralization method, as disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 2004-33984), a neutralizing agent such as sodium hydroxide is added to neutralize the pH to a range of 6-8. Has been proposed. As the aluminum sulfate method, as described in Patent Document 2 (Japanese Patent Laid-Open No. 1-153517), the SO 4 / Al molar ratio is 3/2 to 9/2, and vacuum concentration and cooling are performed. Thus, a method for precipitating aluminum sulfate has been proposed.
溶媒抽出を用いたアルミニウムの抽出方法としては、特許文献３（特開昭６３−２５２１７号公報）に開示されるように、酸性リン酸エステルによるアルミニウムの抽出分離が報告され、無機酸溶液中のアルミニウムの９９％以上が抽出可能だとしている。 As a method for extracting aluminum using solvent extraction, as disclosed in Patent Document 3 (Japanese Patent Laid-Open No. 63-25217), extraction and separation of aluminum by acidic phosphate ester has been reported. More than 99% of aluminum can be extracted.
使用済みリチウムイオン電池リサイクルではアルミニウム含有量の高い原料が存在している。アルミニウム含有量の高い原料を浸出すると、浸出液中にアルミニウムが高濃度で含まれてしまうという問題がある。リチウムイオン電池リサイクルにおける回収対象金属はマンガン、コバルト、ニッケル、リチウムであり、アルミニウムは不純物として分離する必要がある。 In the recycling of used lithium ion batteries, there are raw materials with high aluminum content. When a raw material having a high aluminum content is leached, there is a problem that aluminum is contained in the leachate at a high concentration. Metals to be recovered in lithium ion battery recycling are manganese, cobalt, nickel, and lithium, and aluminum must be separated as impurities.
しかしながら、特許文献１又は２に記載された中和法では、析出した水酸化アルミニウムがゲル化してろ過性を悪化させる他、中和時の共沈作用により液中のコバルトやニッケルも沈殿してしまうという問題がある。硫酸アルミニウム法でも多量の硫酸が必要であるという課題がある。
However, in the neutralization method described in
一方、特許文献３に記載された溶媒抽出法では、アルミニウムは回収できるが、アルミニウムと他の金属との分離方法については報告がなされていない。
On the other hand, in the solvent extraction method described in
そこで、本発明は、アルミニウムとマンガン、その他金属を含む溶液中からアルミニウムを高効率で分離回収可能なアルミニウムの溶媒抽出方法を提供することを課題とする。 Then, this invention makes it a subject to provide the solvent extraction method of aluminum which can isolate | separate and collect aluminum with high efficiency from the solution containing aluminum, manganese, and other metals.
上記課題を解決するために鋭意検討した結果、溶媒抽出法を使用し、抽出時に使用する溶媒として適切な有機溶媒を選択することによって、当該有機溶媒が抽出対象金属により抽出能が異なることを発見し、これを用いてアルミニウムを高効率で分離抽出できることを見出した。 As a result of diligent studies to solve the above problems, it was discovered that by using a solvent extraction method and selecting an appropriate organic solvent as the solvent used during extraction, the extraction ability of the organic solvent differs depending on the metal to be extracted. It was found that aluminum can be separated and extracted with high efficiency by using this.
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、アルミニウムを含む硫酸酸性溶液において、２−エチルヘキシルホスホン酸モノ−２−エチルヘキシルを含む有機溶媒を用いて、アルミニウムを抽出分離する抽出工程を備えるアルミニウムの溶媒抽出方法である。 The present invention completed on the basis of the above knowledge includes, in one aspect, an extraction step of extracting and separating aluminum using an organic solvent containing mono-2-ethylhexyl 2-ethylhexylphosphonate in an acidic solution containing aluminum. It is a solvent extraction method of aluminum.
本発明のアルミニウムの溶媒抽出方法は一実施形態において、前記硫酸酸性溶液が、リチウムイオン電池リサイクルによって得られたアルミニウム含有の浸出液である。 In one embodiment of the method for extracting a solvent of aluminum according to the present invention, the acidic sulfuric acid solution is an aluminum-containing leachate obtained by recycling a lithium ion battery.
本発明のアルミニウムの溶媒抽出方法は更に別の一実施形態において、前記硫酸酸性溶液が、アルミニウム以外の金属として、マンガン、コバルト、ニッケル、リチウムのうち少なくとも一つを含む。 In still another embodiment of the method for extracting a solvent of aluminum according to the present invention, the acidic sulfuric acid solution contains at least one of manganese, cobalt, nickel, and lithium as a metal other than aluminum.
本発明のアルミニウムの溶媒抽出方法は更に別の一実施形態において、前記抽出工程を、平衡ｐＨ１．８以上３以下の条件にて行う。 In still another embodiment of the method for extracting a solvent of aluminum according to the present invention, the extraction step is performed under an equilibrium pH of 1.8 or more and 3 or less.
本発明のアルミニウムの溶媒抽出方法は更に別の一実施形態において、前記硫酸酸性溶液が、少なくともアルミニウムを０．００１〜２０ｇ／Ｌ、マンガンを０．００１〜３０ｇ／Ｌ含む硫酸酸性溶液である。 In still another embodiment of the method for extracting a solvent of aluminum according to the present invention, the sulfuric acid acidic solution is a sulfuric acid acidic solution containing at least 0.001 to 20 g / L of aluminum and 0.001 to 30 g / L of manganese.
本発明のアルミニウムの溶媒抽出方法は更に別の一実施形態において、前記抽出工程を、平衡ｐＨ２以上２．５以下の条件にて行う。 In another embodiment of the method for extracting a solvent of aluminum according to the present invention, the extraction step is performed under an equilibrium pH of 2 or more and 2.5 or less.
本発明によれば、アルミニウムとマンガン、その他金属を含む溶液中からアルミニウムを高効率で分離回収可能なアルミニウムの溶媒抽出方法が提供できる。これにより、例えばリチウムイオン電池リサイクルにおいて、原料を浸出した浸出液中に含まれるアルミニウムを他の金属（マンガン、コバルト、ニッケル、リチウム）をほとんどロスすることなく分離することができる。 ADVANTAGE OF THE INVENTION According to this invention, the solvent extraction method of aluminum which can isolate | separate and collect aluminum with high efficiency from the solution containing aluminum, manganese, and another metal can be provided. Thereby, for example, in lithium ion battery recycling, aluminum contained in the leachate from which the raw material has been leached can be separated with almost no loss of other metals (manganese, cobalt, nickel, lithium).
本発明の実施の形態に係るアルミニウムの溶媒抽出方法は、使用済みのリチウムイオン電池本体から有価金属を回収する方法に好適に利用可能であり、より詳しく述べるならば、リチウムイオン電池に含まれる正極材を処理する際に発生する溶液から溶媒抽出によって不純物であるアルミニウムを抽出分離する方法に利用可能である。以下に、リチウムイオン電池リサイクルにおける浸出液中のアルミニウムを溶媒抽出によって抽出分離する場合を例に説明するが、本発明は以下の例には制限されず、これ以外にもアルミニウムを分離抽出するための様々な用途に利用可能であることは勿論である。 The method for extracting a solvent of aluminum according to an embodiment of the present invention can be suitably used for a method of recovering valuable metals from a used lithium ion battery body, and more specifically, a positive electrode included in a lithium ion battery. The present invention can be used in a method for extracting and separating aluminum as an impurity by solvent extraction from a solution generated when processing a material. In the following, the case where aluminum in the leachate in lithium ion battery recycling is extracted and separated by solvent extraction will be described as an example, but the present invention is not limited to the following examples, and in addition to this, for separating and extracting aluminum Of course, it can be used for various purposes.
＜処理対象液＞
本発明の実施の形態に係るアルミニウムの溶媒抽出方法は、リチウムイオン電池リサイクルにおいて得られたアルミニウム含有の浸出液を処理対象とすることができる。即ち、処理対象液は、アルミニウムの他にリサイクル対象金属であるマンガン、コバルト、ニッケル、リチウム又はその他金属を含む硫酸溶液である。この処理対象液には例えば０．００１〜３００ｇ／Ｌの硫酸、０．００１〜２０ｇ／Ｌのアルミニウム、０．００１〜３０ｇ／Ｌのマンガン、０．００１〜３０ｇ／Ｌのコバルト、０．００１〜３０ｇ／Ｌのニッケル、０．００１〜３０ｇ／Ｌのリチウムが含まれている。
<Processing liquid>
In the solvent extraction method for aluminum according to the embodiment of the present invention, an aluminum-containing leachate obtained in lithium ion battery recycling can be treated. That is, the treatment target liquid is a sulfuric acid solution containing manganese, cobalt, nickel, lithium, or other metals that are recyclable metals in addition to aluminum. For example, 0.001 to 300 g / L sulfuric acid, 0.001 to 20 g / L aluminum, 0.001 to 30 g / L manganese, 0.001 to 30 g / L cobalt, 0.001 ˜30 g / L nickel and 0.001-30 g / L lithium are contained.
この浸出液から溶媒抽出法によってアルミニウムを抽出分離する。抽出剤は２−エチルヘキシルホスホン酸モノ−２−エチルヘキシルを用いる。この抽出剤を炭化水素系溶剤で希釈して調整した溶媒とアルミニウムを含む上記硫酸溶液を混合しアルミニウムの溶媒抽出を行う。２−エチルヘキシルホスホン酸モノ−２−エチルヘキシルと溶剤の混合比は、１：３であるのが好ましい。炭化水素系溶剤としては、芳香族系、パラフィン系、ナフテン系溶剤等が利用可能であり、中でもナフテン系溶剤が好ましい。 Aluminum is extracted and separated from this leachate by a solvent extraction method. As the extractant, 2-ethylhexyl 2-ethylhexylphosphonate is used. A solvent prepared by diluting the extractant with a hydrocarbon solvent and the sulfuric acid solution containing aluminum are mixed to perform solvent extraction of aluminum. The mixing ratio of mono-2-ethylhexyl 2-ethylhexylphosphonate and the solvent is preferably 1: 3. As the hydrocarbon solvent, aromatic, paraffinic, naphthenic solvents and the like can be used, and among them, naphthenic solvents are preferable.
図１に溶媒抽出時の平衡ｐＨと各元素の抽出率との関係を示す。アルミニウム抽出時の平衡ｐＨは、中和剤を添加し、１．８以上、好ましくは２以上、および３以下、好ましくは２．５以下、さらに好ましくは２．３の範囲に調整するのが好ましい。中和剤としては、水酸化ナトリウム、炭酸ナトリウム等を使用することができる。平衡ｐＨが１以上３以下であると溶液中にコバルト、ニッケル、リチウムなどのアルミニウム以外の金属が含まれている場合に、これらアルミニウム以外の金属がアルミニウムと一緒に抽出されるのを抑制し、結果としてアルミニウムをより高効率、かつ、選択的に抽出することができるため、好ましい。特に、溶液中にマンガンが含まれている場合には、平衡ｐＨを２以上２．５以下、好ましくは２．３以下とすることにより、マンガンがアルミニウムと一緒に抽出されるのを抑制し、結果としてアルミニウムをさらに高効率、かつ、選択的に抽出することができるため好ましい。 FIG. 1 shows the relationship between the equilibrium pH at the time of solvent extraction and the extraction rate of each element. The equilibrium pH at the time of aluminum extraction is preferably adjusted to a range of 1.8 or more, preferably 2 or more, and 3 or less, preferably 2.5 or less, more preferably 2.3 by adding a neutralizing agent. . As the neutralizing agent, sodium hydroxide, sodium carbonate or the like can be used. When the equilibrium pH is 1 or more and 3 or less, when a metal other than aluminum such as cobalt, nickel, or lithium is contained in the solution, the metal other than aluminum is prevented from being extracted together with aluminum, As a result, since aluminum can be extracted more efficiently and selectively, it is preferable. In particular, when manganese is contained in the solution, the equilibrium pH is set to 2 or more and 2.5 or less, preferably 2.3 or less to suppress extraction of manganese together with aluminum, As a result, aluminum can be extracted with higher efficiency and selectivity, which is preferable.
抽出工程においてアルミニウムを抽出した溶媒は、酸性溶液で逆抽出する。酸性溶液としては、硫酸溶液、塩酸溶液等が用いられる。図２に逆抽出時の平衡ｐＨとアルミニウムの抽出率との関係を示す。逆抽出時の平衡ｐＨは０〜０．５の範囲に調整するのが好ましい。ｐＨが０．５よりも高いとアルミニウムの逆抽出が不完全で、溶媒中にアルミニウムが残る場合がある。また、ｐＨが０よりも低いと酸濃度が高く、その後の処理が難しくなる。 The solvent from which aluminum has been extracted in the extraction step is back extracted with an acidic solution. As the acidic solution, a sulfuric acid solution, a hydrochloric acid solution, or the like is used. FIG. 2 shows the relationship between the equilibrium pH at the time of back extraction and the extraction rate of aluminum. The equilibrium pH during back extraction is preferably adjusted to a range of 0 to 0.5. If the pH is higher than 0.5, back extraction of aluminum is incomplete and aluminum may remain in the solvent. On the other hand, if the pH is lower than 0, the acid concentration is high, and subsequent processing becomes difficult.
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）
表１に記載の種々の金属を含む硫酸溶液（Ｈ2ＳＯ4濃度１０ｇ／Ｌ）と２−エチルヘキシルホスホン酸モノ−２−エチルヘキシル（大八化学 商品名：ＰＣ−８８Ａ）をナフテン系溶剤（シェルケミカルズ 商品名：ｓｈｅｌｌｓｏｌＤ７０）で２５ｖｏｌ％に希釈調整した溶媒とを有機相／水相＝１（体積比）になるように混合撹拌し、平衡ｐＨ２．３となるように水酸化ナトリウムで調整しながらアルミニウムの抽出を行った。各元素の抽出率を表２に示す。
Example 1
A sulfuric acid solution containing various metals listed in Table 1 (H 2 SO 4 concentration 10 g / L) and 2-ethylhexylphosphonic acid mono-2-ethylhexyl (Daihachi Chemical Co., Ltd., trade name: PC-88A) were added to a naphthenic solvent (shell). Chemicals Product name: Shellsol D70) is mixed and stirred with a solvent diluted to 25 vol% with an organic phase / water phase = 1 (volume ratio), and adjusted with sodium hydroxide so as to have an equilibrium pH of 2.3. Aluminum extraction was performed. Table 2 shows the extraction rate of each element.
（実施例２）
表１に記載の種々の金属を含む硫酸溶液（Ｈ2ＳＯ4濃度１０ｇ／Ｌ）を平衡ｐＨ２．７で実施例１と同様にアルミニウムの抽出を行った。各元素の抽出率を表３に示す。
(Example 2)
In the same manner as in Example 1, aluminum was extracted from a sulfuric acid solution containing various metals shown in Table 1 (H 2 SO 4 concentration: 10 g / L) at an equilibrium pH of 2.7. Table 3 shows the extraction rate of each element.
（実施例３）
表１に記載の種々の金属を含む硫酸溶液（Ｈ2ＳＯ4濃度１０ｇ／Ｌ）を平衡ｐＨ１．９で実施例１と同様にアルミニウムの抽出を行った。各元素の抽出率を表４に示す。
(Example 3)
In the same manner as in Example 1, aluminum was extracted from a sulfuric acid solution containing various metals shown in Table 1 (H 2 SO 4 concentration: 10 g / L) at an equilibrium pH of 1.9. Table 4 shows the extraction rate of each element.
（実施例４〜１８）
表１に記載の種々の金属を含む硫酸溶液（Ｈ2ＳＯ4濃度１０ｇ／Ｌ）を、以下の平衡ｐＨにて、実施例１と同様にアルミニウムの抽出を行い、それぞれ実施例４〜１８とし、平衡ｐＨと各元素の抽出率との関係を図１に示した。
(Examples 4 to 18)
A sulfuric acid solution containing various metals described in Table 1 (H 2 SO 4 concentration 10 g / L) was extracted at the following equilibrium pH in the same manner as in Example 1 to obtain Examples 4 to 18, respectively. The relationship between the equilibrium pH and the extraction rate of each element is shown in FIG.
実施例１〜１８によれば、アルミニウムが他の金属よりも高効率で抽出されることが分かる。特に、平衡ｐＨが１〜３の間では、抽出対象の金属により抽出能が異なることが示され、アルミニウムが選択的に抽出されることが分かる。さらに、平衡ｐＨが２〜２．５、特に２〜２．３の間では、マンガンよりもアルミニウムが顕著に選択的に抽出されることが分かる。 According to Examples 1-18, it turns out that aluminum is extracted more efficiently than another metal. In particular, when the equilibrium pH is between 1 and 3, it can be seen that the extraction ability varies depending on the metal to be extracted, and aluminum is selectively extracted. Furthermore, it can be seen that aluminum is significantly more selectively extracted than manganese when the equilibrium pH is between 2 and 2.5, particularly between 2 and 2.3.
（参考例）
実施例１において溶媒中に抽出されたアルミニウムを逆抽出するため、硫酸溶液（Ｈ2ＳＯ4濃度２０ｇ／Ｌ）を用いて有機相／水相＝１（体積比）、平衡ｐＨ０．４８で逆抽出を行った。溶媒からのアルミニウム逆抽出率を表６に示す。表６より、溶媒中に含まれたアルミニウムの９３％が逆抽出され、溶媒中のアルミニウムを逆抽出するには平衡ｐＨ０．５以下が必要であるということが分かる。
(Reference example)
In order to back-extract the aluminum extracted in the solvent in Example 1, using a sulfuric acid solution (H 2 SO 4 concentration 20 g / L), the organic phase / water phase = 1 (volume ratio) and reverse at an equilibrium pH of 0.48. Extraction was performed. Table 6 shows the rate of aluminum back extraction from the solvent. From Table 6, it can be seen that 93% of the aluminum contained in the solvent is back-extracted and that an equilibrium pH of 0.5 or less is required to back-extract the aluminum in the solvent.
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| WO2023229007A1 (en) * | 2022-05-27 | 2023-11-30 | 株式会社アサカ理研 | Method for extracting aluminum |
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