JP2014037606A - Cobalt extractant and cobalt extraction method - Google Patents
Cobalt extractant and cobalt extraction method Download PDFInfo
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 133
- 239000010941 cobalt Substances 0.000 title claims abstract description 133
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 238000000605 extraction Methods 0.000 title claims abstract description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 52
- 239000011572 manganese Substances 0.000 claims abstract description 52
- 239000003929 acidic solution Substances 0.000 claims abstract description 25
- 150000001412 amines Chemical class 0.000 claims abstract description 18
- 150000002923 oximes Chemical class 0.000 claims abstract description 13
- 238000000638 solvent extraction Methods 0.000 claims abstract description 11
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims abstract description 10
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003141 primary amines Chemical group 0.000 claims abstract description 8
- 239000000284 extract Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 17
- 239000000243 solution Substances 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 230000002378 acidificating effect Effects 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 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 description 4
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000002079 cooperative effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000009916 joint effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 nickel metal hydride Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
本発明は、コバルト抽出剤及びコバルト抽出方法に関する。 The present invention relates to a cobalt extractant and a cobalt extraction method.
コバルトは、二次電池の正極材のほか、航空機のジェットエンジン等に使用されるスーパーアロイ（高強度耐熱合金）等、産業で様々な用途として用いられている。近年、省エネルギーが強く推進されており、自動車業界においては、従来のガソリン車から、コバルトを使用した二次電池を搭載したハイブリッド車や電気自動車への移行が急速に進んでいる。 Cobalt is used for various applications in industries such as superalloys (high strength heat-resistant alloys) used in aircraft jet engines and the like, in addition to positive electrode materials for secondary batteries. In recent years, energy conservation has been strongly promoted, and in the automobile industry, a shift from a conventional gasoline vehicle to a hybrid vehicle or an electric vehicle equipped with a secondary battery using cobalt is rapidly progressing.
上記の工業製品は、耐用年数が過ぎると、使用済み製品として大量に廃棄物になることが予想される。しかし、コバルトは希少資源であり、そのほとんどを輸入に頼っていることから、コバルトを使用済み製品からリサイクルせずに廃棄物にすることは資源節約や資源セキュリティーの観点から好ましくない。最近ではこのような使用済み製品からコバルトを効果的に回収する方法を確立することが強く望まれている。 The above-mentioned industrial products are expected to become a large amount of waste as used products after their useful lives have passed. However, since cobalt is a scarce resource and most of it relies on imports, it is not preferable from the viewpoint of resource saving and resource security to make cobalt a waste product without recycling it from used products. Recently, it has been strongly desired to establish a method for effectively recovering cobalt from such used products.
ところで、上記の二次電池として、ニッケル水素電池やリチウムイオン電池等が挙げられ、これらの正極剤には、希少金属であるコバルトの他にマンガンが使用されている。そして、リチウムイオン電池の正極材においては、高価なコバルトに替わって安価なマンガンの比率を高くする傾向にある。最近では使用済み電池から有価金属の回収が試みられており、回収法の一つとして使用済み電池を炉に投入して溶解させ、メタルとスラグに分離してメタルを回収する乾式法がある。しかし、この方法ではマンガンはスラグに移行するため、コバルトのみしか回収できない。 By the way, as said secondary battery, a nickel metal hydride battery, a lithium ion battery, etc. are mentioned, Manganese other than cobalt which is a rare metal is used for these positive electrode agents. And in the positive electrode material of a lithium ion battery, it tends to increase the ratio of inexpensive manganese instead of expensive cobalt. Recently, recovery of valuable metals from used batteries has been attempted. As one of the recovery methods, there is a dry method in which used batteries are put into a furnace and dissolved, and separated into metal and slag to recover the metal. However, in this method, since manganese is transferred to slag, only cobalt can be recovered.
その他、使用済み電池を酸に溶解して沈澱法、溶媒抽出法、電解採取等の分離方法を用いて金属を回収する湿式法も知られている。例えば、沈澱法では、コバルトとマンガンを含む溶液のｐＨを調整し、硫化剤を添加してコバルトの硫化澱物を得る方法や酸化剤を添加することでマンガンの酸化物澱物を得る方法が知られている（特許文献１参照）。しかし、この方法では、共沈が発生する等の課題があり、コバルトとマンガンとを完全に分離することは難しい。 In addition, a wet method is also known in which a used battery is dissolved in an acid, and a metal is recovered using a separation method such as a precipitation method, a solvent extraction method, or electrolytic collection. For example, in the precipitation method, there are a method of adjusting the pH of a solution containing cobalt and manganese, a method of obtaining a cobalt sulfide starch by adding a sulfurizing agent, and a method of obtaining a manganese oxide starch by adding an oxidizing agent. It is known (see Patent Document 1). However, this method has problems such as coprecipitation, and it is difficult to completely separate cobalt and manganese.
また、電解採取法によってコバルトをメタルとして回収しようとした場合、高濃度のマンガンが存在する系では陽極表面にマンガン酸化物が析出し、陽極の劣化が促進されることが知られている。また、特有の着色した微細なマンガン酸化物が電解液中に浮遊し、電解採取で使用する濾布の目詰まりや、マンガン酸化物によるコバルトメタルの汚染を生じる等、安定した操業が難しい。 Further, it is known that when cobalt is recovered as a metal by electrolytic collection, manganese oxide is deposited on the anode surface in a system in which a high concentration of manganese is present, and the deterioration of the anode is promoted. In addition, the specific colored fine manganese oxide floats in the electrolytic solution, and the filter cloth used for electrolytic collection is clogged, and the cobalt metal is contaminated with the manganese oxide, so that stable operation is difficult.
また、溶媒抽出法を用いてコバルトを回収しようとした場合、酸性抽出剤が広く用いられている。しかし、前述したように、最近ではリチウムイオン電池の正極剤に多くのマンガンが使用されていることから、電池の溶解液は高濃度のマンガンが存在し、このような系からコバルトを選択的かつ効果的に抽出する効果的な抽出剤は無い状況である。 Moreover, when trying to collect cobalt using a solvent extraction method, an acidic extractant is widely used. However, as described above, since a large amount of manganese is recently used in the positive electrode of lithium ion batteries, the battery solution contains a high concentration of manganese. There is no effective extractant to extract effectively.
ところで、２種類以上の抽出剤を混合して用いる場合、１種類の抽出剤を単独で用いる場合とは抽出挙動が変わることがある。このことを協同効果（共同効果ともいう）と呼んでいる。協同効果として、２種類以上の抽出剤を混合して用いることで、１種類の抽出剤を単独で用いる場合に比べて高収率で無電解ニッケル廃液からニッケルを回収できることが提案されている（特許文献２参照）。特許文献２に記載の発明によると、１種類の抽出剤を単独で用いる場合はニッケルをほとんど抽出できないにもかかわらず、２種類以上の抽出剤を混合して用いることで、ｐＨ調整を行うことなく、１回のバッチ抽出で９８〜９９％のニッケルを回収できる。 By the way, when two or more kinds of extractants are mixed and used, the extraction behavior may be different from the case of using one kind of extractant alone. This is called a cooperative effect (also called a joint effect). As a cooperative effect, it has been proposed that two or more kinds of extractants can be mixed and used to recover nickel from electroless nickel waste liquor in a higher yield than when one kind of extractant is used alone ( Patent Document 2). According to the invention described in Patent Document 2, when one type of extractant is used alone, the pH can be adjusted by mixing and using two or more types of extractants even though nickel can hardly be extracted. In addition, 98 to 99% of nickel can be recovered by one batch extraction.
また、カルボン酸系の抽出剤と、オキシム系の抽出剤とを混合し、コバルト、マンガン、カルシウム及びマグネシウムの混合溶液からコバルト及びマンガンを抽出することが提案されている（特許文献３参照）。 It has also been proposed to extract a cobalt and manganese from a mixed solution of cobalt, manganese, calcium and magnesium by mixing a carboxylic acid-based extractant and an oxime-based extractant (see Patent Document 3).
しかしながら、従来の溶媒抽出法では、コバルト、マンガン、カルシウム及びマグネシウムの混合溶液からコバルト及びマンガンを抽出できるにとどまり、コバルト及びマンガンの混合物からマンガンだけを選択的に抽出することは難しい。使用済み電池のリサイクルの他、現在コバルトを生産するために行われているコバルト製錬では原料がニッケル酸化鉱等のニッケル鉱石であるが、ニッケル酸化鉱にはコバルトに比してマンガンの比率が高く、その存在比率はコバルトの５〜１０倍程度である。そのため、コバルトを製錬するにあたり、コバルトとマンガンとの混合物からコバルトを選択的に抽出することは大きな課題となっている。 However, conventional solvent extraction methods can only extract cobalt and manganese from a mixed solution of cobalt, manganese, calcium and magnesium, and it is difficult to selectively extract only manganese from a mixture of cobalt and manganese. In addition to recycling used batteries, cobalt smelting currently used to produce cobalt is made of nickel ore such as nickel oxide ore, but nickel oxide ore has a manganese ratio compared to cobalt. The existence ratio is about 5 to 10 times that of cobalt. Therefore, in refining cobalt, it is a big subject to selectively extract cobalt from a mixture of cobalt and manganese.
本発明は、マンガンを高濃度に含む酸性溶液からコバルトを選択的に抽出できるコバルト抽出剤及びこのコバルト抽出剤を用いたコバルト抽出方法を提供することを目的とする。 An object of the present invention is to provide a cobalt extractant capable of selectively extracting cobalt from an acidic solution containing manganese at a high concentration, and a cobalt extraction method using the cobalt extractant.
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、アミン系抽出剤とオキシム系抽出剤との混合物を用いることで上記の目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by using a mixture of an amine-based extractant and an oxime-based extractant, and to complete the present invention. It came.
具体的には、本発明では、以下のようなものを提供する。 Specifically, the present invention provides the following.
（１）本発明は、アミン系抽出剤とオキシム系抽出剤とを含有するコバルト抽出剤である。 (1) The present invention is a cobalt extractant containing an amine extractant and an oxime extractant.
（２）また、本発明は、前記アミン系抽出剤が１級アミン系抽出剤である、（１）に記載のコバルト抽出剤である。 (2) Moreover, this invention is a cobalt extractant as described in (1) whose said amine extractant is a primary amine extractant.
（３）また、本発明は、前記１級アミン系抽出剤がターシャルブチルアミン及び／又はオクチルアミンを含有する、（２）に記載のコバルト抽出剤である。 (3) Moreover, this invention is a cobalt extractant as described in (2) in which the said primary amine type extractant contains tertiary butylamine and / or octylamine.
（４）また、本発明は、マンガン及びコバルトを含有する酸性溶液を、（１）から（３）のいずれかに記載のコバルト抽出剤による溶媒抽出に付し、前記酸性溶液から前記コバルトを抽出するコバルト抽出方法である。 (4) Moreover, this invention attaches | subjects the acidic solution containing manganese and cobalt to the solvent extraction by the cobalt extractant in any one of (1) to (3), and extracts the said cobalt from the said acidic solution This is a cobalt extraction method.
（５）また、本発明は、前記酸性溶液のｐＨを４．０以上、６．０以下の範囲に調整した後に前記酸性溶液を前記溶媒抽出に付す、（４）に記載のコバルト抽出方法である。 (5) Further, the present invention provides the cobalt extraction method according to (4), wherein the acidic solution is subjected to the solvent extraction after adjusting the pH of the acidic solution to a range of 4.0 or more and 6.0 or less. is there.
本発明によって、高濃度のマンガンを含む溶液からコバルトを選択的かつ工業的に分離するのに適した抽出剤及び操業方法を得ることができる。 According to the present invention, an extractant and an operation method suitable for selectively and industrially separating cobalt from a solution containing a high concentration of manganese can be obtained.
以下、本発明の具体的な実施形態について詳細に説明するが、本発明は以下の実施形態に何ら限定されるものではなく、本発明の目的の範囲内において、適宜変更を加えて実施することができる。 Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. Can do.
＜コバルト抽出剤＞
本発明におけるコバルト抽出剤は、アミン系抽出剤とオキシム系抽出剤との混合物である。アミン系抽出剤は官能基が１級アミンであれば、どのような構造のものでも構わない。具体的には、ターシャルブチルアミンやモノオクチルアミンのほか、ＰＲＩＭＥＮＥ（登録商標）ＪＭ−Ｔ型（ダウケミカル社製）等が挙げられる。これらの１級アミンは単独で用いてもよいし、２種類以上を混合して用いてもよい。
<Cobalt extractant>
The cobalt extractant in the present invention is a mixture of an amine extractant and an oxime extractant. The amine extractant may have any structure as long as the functional group is a primary amine. Specifically, in addition to tertiary butylamine and monooctylamine, PRIMENE (registered trademark) JM-T type (manufactured by Dow Chemical Company) and the like can be mentioned. These primary amines may be used alone or in combination of two or more.
オキシム系抽出剤は、官能基にオキシムを持つものであればケトキシム、アルドキシムなどの形態は問わず、どのような構造であってもよい。市販品として、ケトキシムである５，８−ジエチル−７−ヒドロキシ−６−ドデカンオキシム（商品名：ＬＩＸ６３，コグニス社製）等が知られている。 The oxime-based extractant may have any structure regardless of the form of ketoxime, aldoxime, etc., as long as it has an oxime in the functional group. As a commercially available product, ketoxime 5,8-diethyl-7-hydroxy-6-dodecane oxime (trade name: LIX63, manufactured by Cognis) is known.
アミン系抽出剤とオキシム系抽出剤とのモル比は、２０：８０〜８０：２０であればよいが、工業生産としての実用性が高まる点で４０：６０〜６０：４０であることが好ましい。また、高濃度のマンガンを含む溶液からコバルトだけをより選択的に抽出できる点で、５０：５０であることがより好ましい。 The molar ratio of the amine-based extractant to the oxime-based extractant may be 20:80 to 80:20, but is preferably 40:60 to 60:40 in terms of increasing practicality as industrial production. . Moreover, it is more preferable that it is 50:50 at the point which can extract only cobalt from the solution containing a high concentration manganese more selectively.
また、通常、抽出剤は粘度が高く、そのまま溶媒抽出に使用した場合、水相との相分離性が悪くなるなど操業面への悪影響がある。粘度を下げるため、抽出剤を希釈剤で希釈することが一般的に行われる。希釈剤は、抽出剤と、有価金属であるコバルトの錯体とを溶解できるものであればどのようなものであってもよく、例えば、クロロホルム、ジクロロメタン等の塩素系溶媒、ベンゼン、トルエン、キシレン等の芳香族炭化水素、ヘキサン等の脂肪族炭化水素等が挙げられる。希釈剤は、単独でも複数混合しても良く、１−オクタノールのようなアルコール類を混合しても良い。 In general, the extractant has a high viscosity, and when used as it is for solvent extraction, there are adverse effects on the operation, such as poor phase separation from the aqueous phase. In order to reduce the viscosity, it is common to dilute the extractant with a diluent. The diluent may be any as long as it can dissolve the extractant and the complex of cobalt, which is a valuable metal, for example, chlorinated solvents such as chloroform and dichloromethane, benzene, toluene, xylene and the like. And aromatic hydrocarbons such as hexane and the like. The diluents may be used alone or in combination, and alcohols such as 1-octanol may be mixed.
＜コバルト抽出方法＞
上記のコバルト抽出剤を用いてコバルトを抽出するには、コバルトイオンを含む酸性水溶液を調整し、この酸性水溶液と上記コバルト抽出剤とを混合して撹拌する。その後、混合溶液の水相と有機相とを分液漏斗で分離することで、有機相にコバルトイオンを選択的に抽出することができる。
<Cobalt extraction method>
In order to extract cobalt using the cobalt extractant, an acidic aqueous solution containing cobalt ions is prepared, and the acidic aqueous solution and the cobalt extractant are mixed and stirred. Thereafter, cobalt ions can be selectively extracted into the organic phase by separating the aqueous phase and the organic phase of the mixed solution with a separatory funnel.
酸性水溶液に含まれるコバルト及びマンガンの比率は、コバルト１重量部に対してマンガン５０重量部未満であれば、どのような比率であってもよい。マンガンの量がコバルト１重量部に対して５０質量部を超えると、コバルトだけでなく、マンガンも抽出されてしまう可能性があるため、好ましくない。 The ratio of cobalt and manganese contained in the acidic aqueous solution may be any ratio as long as it is less than 50 parts by weight of manganese with respect to 1 part by weight of cobalt. If the amount of manganese exceeds 50 parts by mass with respect to 1 part by weight of cobalt, not only cobalt but also manganese may be extracted, which is not preferable.
コバルトとマンガンを含有する酸性水溶液から、コバルトを効率的に回収するためには、コバルトとマンガンを含む酸性水溶液のｐＨを４．０以上、６．０以下に調整した後に、上記コバルト抽出剤を加えることが好ましい。ｐＨが４．０未満であると、コバルトを十分に抽出できない可能性があるため、好ましくない。ｐＨが６．０を超えると、コバルトだけでなく、マンガンも抽出されてしまう可能性があるため、好ましくない。 In order to efficiently recover cobalt from an acidic aqueous solution containing cobalt and manganese, the pH of the acidic aqueous solution containing cobalt and manganese is adjusted to 4.0 or more and 6.0 or less, and then the cobalt extractant is used. It is preferable to add. If the pH is less than 4.0, cobalt may not be sufficiently extracted, which is not preferable. If the pH exceeds 6.0, not only cobalt but also manganese may be extracted, which is not preferable.
撹拌は、コバルト抽出剤と酸性水溶液とを混合したときに有機相と水相とが分離しない程度に充分な回転数で行えばよい。酸性水溶液からコバルトを高収率で抽出できるようにするため、撹拌時間は、２０分以上であることが好ましい。その際、水溶液中のｐＨが低下するため、適宜、アルカリ水溶液を添加して所定のｐＨに維持する。 Stirring may be performed at a sufficient number of revolutions such that the organic phase and the aqueous phase are not separated when the cobalt extractant and the acidic aqueous solution are mixed. The stirring time is preferably 20 minutes or longer so that cobalt can be extracted from the acidic aqueous solution in a high yield. At this time, since the pH in the aqueous solution decreases, an aqueous alkaline solution is appropriately added to maintain the pH at a predetermined level.
以下、実施例により、本発明をさらに詳細に説明するが、本発明はこれらの記載に何ら制限を受けるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention does not receive a restriction | limiting at all in these description.
＜実施例１〜５、比較例１〜５：アミン系抽出剤がターシャルブチルアミンである場合＞
［ターシャルブチルアミン含有コバルト抽出剤の調製］
アミン系抽出剤としてターシャルブチルアミンを使用し、オキシム系抽出剤として上記ＬＩＸ６３を使用した。ターシャルブチルアミン及びＬＩＸ６３のいずれもが０．５ｍｏｌ／ｌとなるように各々の抽出剤をトルエンに溶解させることで、本発明に係るターシャルブチルアミン含有コバルト抽出剤（以下、「コバルト抽出剤Ａ」という。）を得た。
<Examples 1 to 5 and Comparative Examples 1 to 5: When the amine-based extractant is tertiary butylamine>
[Preparation of cobalt extractant containing tertiary butylamine]
Tertiary butylamine was used as an amine extractant, and the above LIX63 was used as an oxime extractant. Each of the extractants is dissolved in toluene so that both of the tertiary butylamine and LIX63 are 0.5 mol / l, whereby the tertiary butylamine-containing cobalt extractant (hereinafter referred to as “cobalt extractant A”) according to the present invention is used. It was obtained.
［至適ｐＨの検討］
マンガンを５．０ｇ／ｌと、コバルトを０．１ｇ／ｌとを含み、表１に示す値にｐＨが調整された硫酸水溶液２０ｍｌと、上記コバルト抽出剤Ａ２０ｍｌとを混合し、回転数６５０ｒｐｍで２０分間撹拌した。このとき、硫酸水溶液中のｐＨを表１に示す値に維持するため、１ｍｏｌ／ｌの水酸化ナトリウム水溶液を適宜添加した。その後、混合溶液の水相と有機相とを分液漏斗で分離し、抽出残液（水相）に対して、誘導プラズマ発光分光分析装置（ＩＣＰ−ＡＥＳ）を用いた元素分析を行うことによって、コバルト及びマンガンの水相から有機相への抽出率と、マンガンに対するコバルトの分離係数（コバルト／マンガン）とを求めた。結果を表２に示す。また、ｐＨと抽出率との関係を図１に示し、ｐＨと分離係数との関係を図２に示す。 20 ml of sulfuric acid aqueous solution containing 5.0 g / l of manganese and 0.1 g / l of cobalt and having the pH adjusted to the values shown in Table 1 and 20 ml of the above cobalt extractant A are mixed and rotated at 650 rpm. Stir for 20 minutes. At this time, in order to maintain the pH in the sulfuric acid aqueous solution at the value shown in Table 1, a 1 mol / l sodium hydroxide aqueous solution was appropriately added. Thereafter, the aqueous phase and the organic phase of the mixed solution are separated by a separatory funnel, and the extraction residual liquid (aqueous phase) is subjected to elemental analysis using an induction plasma emission spectrometer (ICP-AES). The extraction rate of cobalt and manganese from the aqueous phase to the organic phase and the separation factor of cobalt from manganese (cobalt / manganese) were determined. The results are shown in Table 2. Moreover, the relationship between pH and an extraction rate is shown in FIG. 1, and the relationship between pH and a separation factor is shown in FIG.
酸性溶液のｐＨを４．０以上６．０以下の範囲に調整した後に溶媒抽出に付すと、極めて高濃度（コバルトの５０倍）の濃度のマンガンを含むコバルト／マンガンの混合溶液からコバルトだけを高収率かつ高純度で回収できることが確認された（実施例１〜５）。 When the pH of the acidic solution is adjusted to a range of 4.0 or more and 6.0 or less and then subjected to solvent extraction, only cobalt from a cobalt / manganese mixed solution containing manganese at a very high concentration (50 times that of cobalt) is obtained. It was confirmed that it can be recovered with high yield and high purity (Examples 1 to 5).
一方、酸性溶液のｐＨが４．０未満であると、コバルトの抽出率が３０％以下であり、コバルト／マンガンの混合溶液からコバルトを高収率で回収できない可能性があることが確認された（比較例１〜３）。また、酸性溶液のｐＨを４．０以下であると、分離係数も低いことが確認された。 On the other hand, when the pH of the acidic solution is less than 4.0, the extraction rate of cobalt is 30% or less, and it was confirmed that cobalt may not be recovered in a high yield from the cobalt / manganese mixed solution. (Comparative Examples 1-3). It was also confirmed that the separation factor was low when the pH of the acidic solution was 4.0 or less.
そして、酸性溶液のｐＨが６．０を超える場合、マンガンの抽出率が２０％以上となる。すなわち、酸性溶液のｐＨが６．０を超える場合、コバルトだけでなく、マンガンも抽出され得ることが確認された（比較例４、５）。これは、コバルトを抽出した有機溶媒に対して逆抽出を行って精製コバルト水溶液を得ようとした場合、コバルトと同時に逆抽出されるマンガンによる汚染が酷くなることから好ましい条件ではない。 And when the pH of an acidic solution exceeds 6.0, the extraction rate of manganese will be 20% or more. That is, when the pH of the acidic solution exceeded 6.0, it was confirmed that not only cobalt but also manganese could be extracted (Comparative Examples 4 and 5). This is not a preferable condition because when a reverse cobalt extraction is performed on an organic solvent from which cobalt is extracted to obtain a purified cobalt aqueous solution, contamination by manganese that is back extracted simultaneously with cobalt becomes severe.
以上のように、コバルト濃度の５０倍にも達するような極めて高濃度の濃度のマンガンを含有したコバルト・マンガンの混合した酸性水溶液を、ｐＨが４．０以上、６．０以下になるように調整し、当該酸性水溶液を、オキシム系抽出剤とアミン系抽出剤の混合溶媒を用いて溶媒抽出を行うことでコバルトを高純度かつ高収率で抽出でき、工業生産としての実用性も高いことが確認された。 As described above, an acidic aqueous solution containing cobalt and manganese containing manganese at a very high concentration that reaches 50 times the cobalt concentration is adjusted so that the pH is 4.0 or more and 6.0 or less. Cobalt can be extracted with high purity and high yield by adjusting the acid aqueous solution using a mixed solvent of oxime-based extractant and amine-based extractant, and it is also highly practical for industrial production. Was confirmed.
＜実施例６〜８、比較例６、７：アミン系抽出剤がモノオクチルアミンである場合＞
［モノオクチルアミン含有コバルト抽出剤の調製］
アミン系抽出剤としてモノオクチルアミンを使用し、オキシム系抽出剤として上記ＬＩＸ６３を使用した。モノオクチルアミン及びＬＩＸ６３のいずれもが０．５ｍｏｌ／ｌとなるように各々の抽出剤をトルエンに溶解させることで、本発明に係るモノオクチルアミン含有コバルト抽出剤（以下、「コバルト抽出剤Ｂ」という。）を得た。
<Examples 6 to 8, Comparative Examples 6 and 7: When the amine-based extractant is monooctylamine>
[Preparation of monooctylamine-containing cobalt extractant]
Monooctylamine was used as the amine extractant, and the above LIX63 was used as the oxime extractant. By dissolving each extractant in toluene so that both monooctylamine and LIX63 are 0.5 mol / l, the monooctylamine-containing cobalt extractant (hereinafter, “cobalt extractant B”) according to the present invention is used. It was obtained.
［至適ｐＨの検討］
コバルト抽出剤としてコバルト抽出剤Ｂを用い、硫酸水溶液中のｐＨを表３に示す値に維持させたこと以外は、実施例１と同じ方法にて、コバルト及びマンガンの水相から有機相への抽出率と、マンガンに対するコバルトの分離係数（コバルト／マンガン）とを求めた。結果を表４に示す。また、ｐＨと抽出率との関係を図３に示し、ｐＨと分離係数との関係を図４に示す。 Using the cobalt extractant B as the cobalt extractant and maintaining the pH in the sulfuric acid aqueous solution at the value shown in Table 3, the same method as in Example 1 was used to convert the cobalt and manganese aqueous phase to the organic phase. The extraction rate and the separation factor of cobalt relative to manganese (cobalt / manganese) were determined. The results are shown in Table 4. Moreover, the relationship between pH and an extraction rate is shown in FIG. 3, and the relationship between pH and a separation factor is shown in FIG.
酸性溶液のｐＨを４．０以上６．０以下の範囲に調整した後に溶媒抽出に付すと、極めて高濃度（コバルトの５０倍）の濃度のマンガンを含むコバルト／マンガンの混合溶液からコバルトだけを高収率かつ高純度で回収できることが確認された（実施例６〜８）。 When the pH of the acidic solution is adjusted to a range of 4.0 or more and 6.0 or less and then subjected to solvent extraction, only cobalt from a cobalt / manganese mixed solution containing manganese at a very high concentration (50 times that of cobalt) is obtained. It was confirmed that it can be recovered with high yield and high purity (Examples 6 to 8).
一方、酸性溶液のｐＨが４．０未満であると、例えば、比較例６の場合はコバルトの抽出率が９％であり、コバルト／マンガンの混合溶液からコバルトを高収率で回収できない可能性があることが確認された。また、酸性溶液のｐＨを４．０以下であると、分離係数も低いことが確認された。 On the other hand, if the pH of the acidic solution is less than 4.0, for example, in the case of Comparative Example 6, the extraction rate of cobalt is 9%, and there is a possibility that cobalt cannot be recovered from the cobalt / manganese mixed solution in a high yield. It was confirmed that there is. It was also confirmed that the separation factor was low when the pH of the acidic solution was 4.0 or less.
そして、酸性溶液のｐＨが６．０を超える場合、例えば、比較例７の場合はコバルトの抽出率が１９％であり、コバルトだけでなく、マンガンも抽出され得ることが確認された。これは、コバルトを抽出した有機溶媒に対して逆抽出を行って精製コバルト水溶液を得ようとした場合、コバルトと同時に逆抽出されるマンガンによる汚染が酷くなることから好ましい条件ではない。 Then, when the pH of the acidic solution exceeds 6.0, for example, in the case of Comparative Example 7, it was confirmed that the extraction rate of cobalt was 19%, and not only cobalt but also manganese could be extracted. This is not a preferable condition because when a reverse cobalt extraction is performed on an organic solvent from which cobalt is extracted to obtain a purified cobalt aqueous solution, contamination by manganese that is back extracted simultaneously with cobalt becomes severe.
以上のように、コバルト濃度の５０倍にも達するような極めて高濃度の濃度のマンガンを含有したコバルト・マンガンの混合した酸性水溶液を、ｐＨが４．０以上、６．０以下になるように調整し、当該酸性水溶液を、オキシム系抽出剤とアミン系抽出剤の混合溶媒を用いて溶媒抽出を行うことでコバルトを高純度かつ高収率で抽出でき、工業生産としての実用性も高いことが確認された。 As described above, an acidic aqueous solution containing cobalt and manganese containing manganese at a very high concentration that reaches 50 times the cobalt concentration is adjusted so that the pH is 4.0 or more and 6.0 or less. Cobalt can be extracted with high purity and high yield by adjusting the acid aqueous solution using a mixed solvent of oxime-based extractant and amine-based extractant, and it is also highly practical for industrial production. Was confirmed.
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| JPS59208028A (en) * | 1983-05-11 | 1984-11-26 | Nippon Mining Co Ltd | Organic liquid extracting reagent for extracting metal |
| JPH07150262A (en) * | 1993-11-26 | 1995-06-13 | Japan Energy Corp | Decomposition preventive method of extracting agent |
| JP2011038182A (en) * | 1998-12-12 | 2011-02-24 | Cytec Technology Corp | Solvent extraction composition, and method therefor |
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| JPS59208028A (en) * | 1983-05-11 | 1984-11-26 | Nippon Mining Co Ltd | Organic liquid extracting reagent for extracting metal |
| JPH07150262A (en) * | 1993-11-26 | 1995-06-13 | Japan Energy Corp | Decomposition preventive method of extracting agent |
| JP2011038182A (en) * | 1998-12-12 | 2011-02-24 | Cytec Technology Corp | Solvent extraction composition, and method therefor |
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