JP5120929B2 - Method for producing metal nanoparticles using reverse micelle liquid-liquid extraction method - Google Patents
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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
Description
本発明は、廃液などの水溶液から、金などの金属ナノ粒子を製造する方法に関する。さらに詳細には、本発明は、水と有機溶媒などの抽出媒体から成る２液相系の抽出媒体相中で生成する逆ミセルと呼ばれるナノ反応場を利用して、金属ナノ粒子を製造する方法に関する。 The present invention relates to a method for producing metal nanoparticles such as gold from an aqueous solution such as a waste liquid. More specifically, the present invention relates to a method for producing metal nanoparticles by utilizing a nano-reaction field called reverse micelle generated in a two-liquid phase extraction medium phase composed of an extraction medium such as water and an organic solvent. About.
初めに、逆ミセルとは、不活性媒体（アルカン、超臨界流体二酸化炭素など）中で生成する界面活性剤の集合体であり、多くの場合、その内側には内核水相と呼ばれるナノメーターサイズの微小水滴を有する。別の言い方をすると、逆ミセルとは、界面活性剤の形成する単分子膜に覆われたナノ水滴である。このようなナノ反応場を利用して、金属ナノ粒子を製造する方法は既に広く知られている。この方法は、生成するナノ粒子の均質性が高い、種々の化学反応を利用して多様な形態の粒子を製造できる、粒子の表面を修飾できる、また、穏やかな条件（例えば、室温）でナノ粒子を製造ができるなどの利点があり、ナノ粒子の大量生産にも適している。 First, reverse micelles are a collection of surfactants generated in an inert medium (alkanes, supercritical fluid carbon dioxide, etc.), and are often nanometer-sized, called the inner core aqueous phase. With fine water droplets. In other words, the reverse micelle is a nano water droplet covered with a monomolecular film formed by a surfactant. A method for producing metal nanoparticles using such a nanoreaction field is already widely known. This method has high homogeneity of the produced nanoparticles, can produce various types of particles using various chemical reactions, can modify the surface of the particles, and can be nano-structured under mild conditions (eg, room temperature). It has advantages such as the ability to produce particles and is suitable for mass production of nanoparticles.
さて、このような逆ミセルを利用したナノ粒子製造法（逆ミセル法）として、従来から、微量注入法が知られている。微量注入法とは、ナノ粒子化したい金属イオンを高濃度かつ高純度で含む水溶液を、界面活性剤を含む不活性溶媒に微量注入することによって、高濃度かつ高純度の目的金属イオンを含む逆ミセルを生成させた後、還元剤などを作用させて金属ナノ粒子を生成させる方法である（例えば、非特許文献１を参照）。図1に上述した従来技術である微量注入法の概要を示す。 As a nanoparticle manufacturing method (reverse micelle method) using such reverse micelles, a microinjection method is conventionally known. The micro-injection method is a reverse injection that contains high-concentration and high-purity target metal ions by micro-injecting an aqueous solution containing high-concentration and high-purity metal ions to be nanoparticulate into an inert solvent containing a surfactant. This is a method of generating metal nanoparticles by generating a micelle and then reacting with a reducing agent or the like (see, for example, Non-Patent Document 1). FIG. 1 shows an outline of the microinjection method that is the conventional technique described above.
一方、水相中の金属イオンを有機溶媒などの抽出溶媒相に抽出した後、還元剤などを作用させてナノ粒子を製造する方法（液-液抽出法）がある。例えば、M. Brustらは、水相中のテトラクロロ金酸イオンをトルエン相へ相間移動させる試薬としてテトラアルキルアンモニウム塩を用いることで、２液相系での金ナノ粒子の製造に成功している（例えば、非特許文献２を参照）。 On the other hand, there is a method (liquid-liquid extraction method) in which metal ions in an aqueous phase are extracted into an extraction solvent phase such as an organic solvent and then nanoparticles are produced by acting a reducing agent or the like. For example, M. Brust et al. Succeeded in producing gold nanoparticles in a two-liquid phase system by using a tetraalkylammonium salt as a reagent for transferring a tetrachloroaurate ion in an aqueous phase to a toluene phase. (For example, see Non-Patent Document 2).
また、本願発明者の長縄らは、以前の研究において、界面活性剤と有機配位子を組み合わせて生じる逆ミセル系が、ランタノイドなどの金属イオンに対して非常に大きな抽出機能と優れた選択的分離機能を有することを発見している（例えば、非特許文献３を参照）。
金属ナノ粒子を製造する方法は様々であるが、上述した逆ミセル法(微量注入法)では、例えば工場からの廃水のように、ナノ粒子にしたい金属を僅かにしか含まないうえに多数の他金属が共存する水溶液を原材料として、高品質な金属ナノ粒子を製造することが困難である。一方、上述した液-液抽出法では、目的金属イオンの抽出およびそのナノ粒子化を同じ溶媒相で行うことができ、ナノ粒子化したい目的金属イオンの濃度が希薄な水溶液からであっても目的金属イオンを抽出溶媒中に濃集することでナノ粒子を製造することが可能である。しかしながら、Brust法のような従来の液-液抽出法では、不純物として他金属イオン（例えば、白金族元素、亜鉛、鉄など）が共存する水溶液中からナノ粒子化したい目的金属イオン（例えば、金）だけを選択的に抽出してナノ粒子化することはできない。また、Brust法は、クロロ錯陰イオンを形成する金属以外のナノ粒子化には適用できない。また、Brust法のような従来の液-液抽出法での還元反応には、水素化ホウ素ナトリウムのような強力な還元剤が必要であるが、このような試薬の扱いには危険を伴う。 There are various methods for producing metal nanoparticles, but the reverse micelle method (microinjection method) described above contains only a small amount of metal that is desired to be formed into nanoparticles, such as waste water from a factory. It is difficult to produce high-quality metal nanoparticles using an aqueous solution containing metals as a raw material. On the other hand, in the liquid-liquid extraction method described above, the extraction of the target metal ion and its nanoparticulation can be performed in the same solvent phase, and even if the concentration of the target metal ion desired to be nanoparticulate is from a dilute aqueous solution Nanoparticles can be produced by concentrating metal ions in the extraction solvent. However, in a conventional liquid-liquid extraction method such as the Brust method, a target metal ion (for example, gold) that is desired to be made into nanoparticles from an aqueous solution in which other metal ions (for example, a platinum group element, zinc, iron, etc.) coexist as impurities is present. ) Cannot be selectively extracted into nanoparticles. In addition, the Brust method cannot be applied to the formation of nanoparticles other than metals that form chloro complex anions. In addition, the reduction reaction in the conventional liquid-liquid extraction method such as the Brust method requires a strong reducing agent such as sodium borohydride, but handling such a reagent is dangerous.
逆ミセル法と液-液抽出法を組み合わせることができれば、逆ミセルのナノサイズ反応場を利用して高品質で多様なナノ粒子を製造できるという逆ミセル法の利点と、目的金属イオンの濃度が希薄な水溶液からであっても抽出・濃集することでナノ粒子を製造できるという液-液抽出法の利点の両方を合わせ持つ、新たなナノ粒子製造法が生まれると期待できる。具体的には、水と抽出溶媒から成る２液相系の抽出溶媒相において逆ミセルを形成させ、その逆ミセルに金属イオンを抽出する機能（抽出機能）を持たせれば、逆ミセルをナノ粒子生成の反応場だけではなく、液-液抽出にも利用できる。また、このときの逆ミセルに、目的とする金属イオンを選択的に分離する機能（選択的分離機能）を持たせれば、多数の不純物が共存する水溶液からであっても、目的金属イオンのみを選択的に抽出してナノ粒子化できる。これが可能になれば、従来の液-液抽出を利用した方法（例えば、Brust法）にはなかったメリットになる。これら抽出機能と選択的分離機能を合わせ持つ逆ミセル系（以後、“機能化逆ミセル系”と称する）は、すでに本願発明者によって開発されている（前述の非特許文献３を参照）。図２に模式的に示すように、有機配位子を添加することにより生じる機能化逆ミセル系では、目的金属イオンのみを高選択的に抽出できる。しかし、多数の不純物が共存する水溶液から目的とする金属イオンのみを取り出して、成分、形状および粒径の整った、高品質の金属ナノ粒子を製造するまでには至っていない。 If the reverse micelle method can be combined with the liquid-liquid extraction method, the advantages of the reverse micelle method that the nano-sized reaction field of the reverse micelle can be used to produce a variety of high-quality nanoparticles and the concentration of the target metal ion It can be expected that a new nanoparticle production method will be born that combines both the advantages of liquid-liquid extraction methods, in which nanoparticles can be produced by extraction and concentration even from dilute aqueous solutions. Specifically, if reverse micelles are formed in a two-liquid phase extraction solvent phase consisting of water and extraction solvent, and the reverse micelles have a function of extracting metal ions (extraction function), then the reverse micelles will become nanoparticles. It can be used not only for the reaction field of production but also for liquid-liquid extraction. In addition, if the reverse micelle at this time has a function of selectively separating the target metal ion (selective separation function), only the target metal ion can be obtained even from an aqueous solution in which many impurities coexist. It can be selectively extracted to form nanoparticles. If this becomes possible, it will be a merit not found in conventional methods using liquid-liquid extraction (for example, the Brust method). A reverse micelle system (hereinafter referred to as “functionalized reverse micelle system”) having both the extraction function and the selective separation function has already been developed by the inventor of the present application (see Non-Patent Document 3 described above). As schematically shown in FIG. 2, in the functionalized reverse micelle system generated by adding the organic ligand, only the target metal ion can be extracted with high selectivity. However, it has not yet been possible to produce only high-quality metal nanoparticles having a uniform component, shape and particle size by extracting only the target metal ions from an aqueous solution in which a large number of impurities coexist.
本発明の目的は、逆ミセル法と液-液抽出法の両方の利点を合わせ持ち、かつ目的金属のみを選択的にナノ粒子化できるという、従来法では実現できない優れた特徴を有する新しい金属ナノ粒子の製造方法を提供することにある。 The object of the present invention is to combine the advantages of both the reverse micelle method and the liquid-liquid extraction method, and to selectively form nanoparticles of the target metal only. The object is to provide a method for producing particles.
本願発明者は、前述の課題を解決すべく鋭意研究を重ねた結果、目的金属イオンを逆ミセルに濃集した後、還元剤などを作用させることで高品質の金属ナノ粒子を製造できる方法を開発した。この新しい金属ナノ粒子の製造方法は、言わば逆ミセル法と液-液抽出法を組み合わせた方法であるので、“逆ミセル液-液抽出法”と名付けることにする。 As a result of intensive research to solve the above-mentioned problems, the present inventor has developed a method capable of producing high-quality metal nanoparticles by concentrating target metal ions in reverse micelles and then acting on a reducing agent or the like. developed. Since this new method for producing metal nanoparticles is a method combining the reverse micelle method and the liquid-liquid extraction method, it will be named “reverse micelle liquid-liquid extraction method”.
本発明に係る逆ミセル液-液抽出法を利用した金属ナノ粒子の製造方法は、少なくとも１種以上の目的金属イオンを含む金属水溶液である水相と、界面活性剤および有機配位子を含む不活性溶媒である有機相とを混合し、前記目的金属イオンを逆ミセルに濃集させた後、逆ミセルを含む前記有機相を分取し、分取された前記有機相に還元剤を加えるなどして、一定時間反応させて金属ナノ粒子を生成するステップから成る。生成する金属ナノ粒子が金である場合には、界面活性剤としてＡＯＴ（後述）、有機配位子としてＴＯＤＧＡ（後述）、そして還元剤としてはヒドラジンが好適である。 The method for producing metal nanoparticles using the reverse micelle liquid-liquid extraction method according to the present invention includes an aqueous phase that is an aqueous metal solution containing at least one target metal ion, a surfactant, and an organic ligand. After mixing the organic phase that is an inert solvent and concentrating the target metal ions in reverse micelles, the organic phase containing reverse micelles is fractionated, and a reducing agent is added to the fractionated organic phase. Etc., and reacting for a certain time to form metal nanoparticles. When the metal nanoparticles to be produced are gold, AOT (described later) as the surfactant, TODGA (described later) as the organic ligand, and hydrazine as the reducing agent are suitable.
本発明に係る逆ミセル液-液抽出法を利用した金属ナノ粒子の製造方法によって、ナノ粒子化したい目的の金属イオンが低濃度でかつ不純物として多数の他金属イオンが共存する水溶液中からであっても、目的金属イオンのみを高選択的に逆ミセルに抽出・濃集した後にナノ粒子化することで、廃液のような水溶液から高純度で均質性の高い高品質なナノ粒子を製造することが可能となる。 By the metal nanoparticle production method using the reverse micelle liquid-liquid extraction method according to the present invention, the target metal ion to be nanoparticulate is from an aqueous solution in which many other metal ions coexist as impurities. However, high-quality nanoparticles with high purity and high homogeneity can be produced from aqueous solutions such as waste liquid by extracting and concentrating only the target metal ions in reverse micelles with high selectivity. Is possible.
逆ミセル液-液抽出法では、界面活性剤と有機配位子を組み合わせて用いるが、目的とする金属イオンに対する有機配位子の選択性と界面活性剤が形成する逆ミセルと金属-配位子錯体との親和性から、目的金属イオンに対する抽出機能と選択的分離機能が同時に逆ミセルに付加される。とくに、優れた選択的分離機能は、Brust法のような従来の液-液抽出法にはない特徴である。 The reverse micelle liquid-liquid extraction method uses a combination of surfactant and organic ligand, but the selectivity of the organic ligand for the target metal ion and the reverse micelle and metal-coordination formed by the surfactant. Due to the affinity with the child complex, an extraction function for the target metal ion and a selective separation function are simultaneously added to the reverse micelle. In particular, an excellent selective separation function is a feature not found in conventional liquid-liquid extraction methods such as the Brust method.
また、逆ミセル液-液抽出法では、目的金属イオンに合わせて有機配位子を選択するが、このことは、金属イオンを限定することなく、自由に系を設計できることを意味している。一方、Brust法はクロロ錯陰イオンを形成する金属イオン以外には適用できないので、あらゆる金属イオンに対して適用可能な逆ミセル液-液抽出法は、この点でもBrust法にはないメリットを持つと言える。 In the reverse micelle liquid-liquid extraction method, an organic ligand is selected in accordance with the target metal ion, which means that the system can be freely designed without limiting the metal ion. On the other hand, since the Brust method can only be applied to metal ions that form chloro complex anions, the reverse micelle liquid-liquid extraction method that can be applied to any metal ion has advantages that the Brust method does not have. It can be said.
また、逆ミセル液-液抽出法は、危険な試薬を用いることなく室温での操作でナノ粒子製造ができるという点で、安全面においても有利である。従来法であるBrust法では、例えば金のナノ粒子を作製する際、水相中のテトラクロロ金酸イオンをトルエン相に抽出した後、分取したトルエン相にアルカンチオールを加えてテトラクロロ金酸イオンを安定な錯体にした後、そこに強力な還元剤である水素化ホウ素ナトリウムを作用させることで金ナノ粒子を生成させる。テトラクロロ金酸イオンをアルカンチオールなしで還元すると、金ナノ粒子が生成すると同時に即座に凝集してしまうため、アルカンチオールは必ず還元剤を添加する前に加える必要がある。アルカンチオールはテトラクロロ金酸イオンを安定化する配位子として有効である反面、生成した錯体は容易に還元することができないため、必然的に強力な還元剤が必要になってしまう。一方、逆ミセル液-液抽出法では、逆ミセルという体積の制限された反応場で還元反応を起こすことによって金ナノ粒子が生成する。このとき、１つ１つの金ナノ粒子は逆ミセルというカプセルに閉じ込められた状態で単分散しているので、金ナノ粒子同士が凝集しにくい。すなわち、還元によって金ナノ粒子を生成させた後に、金ナノ粒子にアルカンチオールを化学吸着させて安定化させることができる。このことから、穏やかに反応する還元剤（例えば、ヒドラジン）でも十分に働くため、水素化ホウ素ナトリウムのような水などと激しく反応する強力な試薬を用いる必要がなく、危険を伴わない。 Further, the reverse micelle liquid-liquid extraction method is advantageous in terms of safety in that nanoparticles can be produced by operation at room temperature without using dangerous reagents. In the conventional Brust method, for example, when producing gold nanoparticles, tetrachloroauric acid ions in an aqueous phase are extracted into a toluene phase, and then alkanethiol is added to the separated toluene phase to add tetrachloroauric acid. After making ions into a stable complex, gold nanoparticles are generated by allowing sodium borohydride, which is a strong reducing agent, to act on the complex. When tetrachloroaurate ions are reduced without alkanethiol, gold nanoparticles are formed and immediately aggregated. Therefore, alkanethiol must be added before the reducing agent is added. Alkanethiol is effective as a ligand that stabilizes tetrachloroaurate ions, but the complex produced cannot be reduced easily, so that a strong reducing agent is inevitably required. On the other hand, in the reverse micelle liquid-liquid extraction method, a gold nanoparticle is generated by causing a reduction reaction in a reaction field with a limited volume called reverse micelle. At this time, since each gold nanoparticle is monodispersed in a state of being confined in a capsule called reverse micelle, the gold nanoparticles are unlikely to aggregate. That is, after producing gold nanoparticles by reduction, alkanethiol can be chemically adsorbed to the gold nanoparticles and stabilized. For this reason, a reducing agent that reacts gently (for example, hydrazine) works well, so there is no need to use a strong reagent that reacts violently with water such as sodium borohydride, and there is no danger.
本発明で使用する逆ミセル液-液抽出法の概要を図３に示す。図３から理解されるように、初めに、少なくとも１種以上の目的金属イオンを含む金属水溶液である水相と、界面活性剤および有機配位子を含む不活性溶媒である有機相が準備され、これらが充分に混合される。図３では、混合プロセスを抽出として矢印で示している。混合の結果、ほぼ前記目的金属イオンのみが、逆ミセルに濃集させられる。次に、逆ミセルを含む前記有機相が分取され、分取された前記有機相に還元剤と保護剤が加えられる。この状態で、一定時間反応させると金属ナノ粒子が生成される。これらの各ステップは室温にて行われる。なお、前記還元剤の代わりに、特定の試薬を加えるとか、光や放射線を当てて金属ナノ粒子を生成することも可能である。 An outline of the reverse micelle liquid-liquid extraction method used in the present invention is shown in FIG. As can be understood from FIG. 3, first, an aqueous phase that is an aqueous metal solution containing at least one or more kinds of target metal ions and an organic phase that is an inert solvent containing a surfactant and an organic ligand are prepared. These are mixed thoroughly. In FIG. 3, the mixing process is indicated by an arrow as an extraction. As a result of mixing, only the target metal ions are concentrated in the reverse micelle. Next, the organic phase containing reverse micelles is separated, and a reducing agent and a protective agent are added to the separated organic phase. In this state, when the reaction is performed for a certain time, metal nanoparticles are generated. Each of these steps is performed at room temperature. In addition, it is also possible to produce | generate a metal nanoparticle by adding a specific reagent instead of the said reducing agent, or applying light and a radiation.
この製造方法は、従来の逆ミセル法（微量注入法）とは異なり、純粋で高濃度の目的金属イオンを含む水溶液を用意する必要がなく、廃液のように、目的金属イオンの濃度が低いうえに多くの不純物が含まれる水溶液からであっても、ナノ粒子を製造することができる点に大きな特徴がある。なお、図３においては、この点を強調するために、水相は低濃度で不純物の多い金属水溶液になっているが、当然高濃度であっても、不純物の少ない金属水溶液であっても良いことは明らかである。 Unlike the conventional reverse micelle method (microinjection method), this manufacturing method does not require the preparation of an aqueous solution containing pure and high-concentration target metal ions. Even in an aqueous solution containing a large amount of impurities, there is a great feature in that nanoparticles can be produced. In FIG. 3, in order to emphasize this point, the aqueous phase is a metal aqueous solution with a low concentration and a large amount of impurities, but it may naturally be a high concentration or a metal aqueous solution with few impurities. It is clear.
なお、逆ミセル液-液抽出法では、例えば金のナノ粒子を作製する際、水素化ホウ素ナトリウムのような強力な還元剤を使用する必要がなく、作用が緩やかで安全な還元剤（例えば、ヒドラジン）でも十分であるため、ほとんど危険性がない。また、逆ミセル液-液抽出法には、室温のような穏やかな条件下でナノ粒子が製造できるというメリットもある。 In the reverse micelle liquid-liquid extraction method, for example, when producing gold nanoparticles, it is not necessary to use a strong reducing agent such as sodium borohydride, and a reducing agent that is mild and safe (for example, Hydrazine) is sufficient, so there is almost no danger. The reverse micelle liquid-liquid extraction method also has the advantage that nanoparticles can be produced under mild conditions such as room temperature.
金のナノ粒子は、ナノ触媒、診断薬材料などとして広いニーズを持つ代表的な金属ナノ粒子として知られている。また、金は、実際に、メッキ工場からの廃水などに少量含まれるので、ナノ粒子として再資源化する意義も大きい。そこで、廃水を模擬した金含有水溶液を作製し、金ナノ粒子を製造するための原材料として利用する試験を行った。 Gold nanoparticles are known as typical metal nanoparticles having a wide range of needs such as nanocatalysts and diagnostic materials. In addition, since gold is actually contained in a small amount in waste water from a plating factory, it is highly significant to recycle it as nanoparticles. Then, the gold containing aqueous solution which simulated wastewater was produced, and the test used as a raw material for manufacturing a gold nanoparticle was done.
本発明による逆ミセル液-液抽出法では、界面活性剤と有機配位子を組み合わせて用いる。模擬廃液から金ナノ粒子を製造する試験では、界面活性剤としてビス（ジエチルヘキシル）スルホコハク酸ナトリウム[Bis(2-ethylhexyl)sulfosuccinate sodium salt]（商標名AerosolOT：AOTと略す）、有機配位子としてN,N,N',N'-テトラオクチル-3-オキサペンタン-1,5-ジアミド：テトラオクチルジグリコールアミド[N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide：tetraoctyldiglycolamide]（TODGAと略す）を使用した。下記の実施例に、その詳細を記す。 In the reverse micelle liquid-liquid extraction method according to the present invention, a surfactant and an organic ligand are used in combination. In a test for producing gold nanoparticles from a simulated waste liquid, as a surfactant, sodium bis (diethylhexyl) sulfosuccinate sodium salt (trade name: AerosolOT: AOT) is used as an organic ligand. N, N, N ', N'-Tetraoctyl-3-oxapentane-1,5-diamide: Tetraoctyl diglycolamide [N, N, N', N'-tetraoctyl-3-oxapentane-1,5- diamide: tetraoctyldiglycolamide] (abbreviated as TODGA). The details are described in the following examples.
（実施例1）AOTとTODGAを組み合わせた逆ミセルによる模擬廃液からの金イオンの選択的抽出 (Example 1) Selective extraction of gold ion from simulated waste liquid by reverse micelle combining AOT and TODGA
AOTとTODGAを含むイソオクタン溶液と塩酸水溶液の間の金イオンといくつかの共存金属イオンの液-液分配比を測定した。実験操作を以下に示す。
1）5 mM AOTと10 mM TODGAを含むイソオクタン溶液5 mlとそれぞれ1 ppmの鉄、ニッケル、銅、亜鉛、パラジウム、白金、および金を含む1 M 塩酸水溶液（模擬廃液）5 mlを試験管の中に入れ、ボルテックスミキサーにより、15分間振とうした。
2）5分間の遠心分離の後、水相の一部を採取した。
3）採取した水相を0.5 M硝酸水溶液で希釈し、誘導結合プラズマ質量分析装置（ICP-MS）を用いて、それぞれの金属イオンの濃度を測定した。
4）それぞれの金属イオンについて、初濃度から水相に残った濃度を引き算して有機相に抽出された濃度とし、抽出率（=有機相中の濃度/初濃度）を求めた。
The liquid-liquid partition ratio of gold ions and some coexisting metal ions between isooctane solution containing AOT and TODGA and aqueous hydrochloric acid was measured. The experimental procedure is shown below.
1) 5 ml of isooctane solution containing 5 mM AOT and 10 mM TODGA and 5 ml of 1 M hydrochloric acid solution (simulated waste solution) containing 1 ppm of iron, nickel, copper, zinc, palladium, platinum, and gold, respectively, in a test tube It was put in and shaken with a vortex mixer for 15 minutes.
2) After centrifugation for 5 minutes, a part of the aqueous phase was collected.
3) The collected aqueous phase was diluted with a 0.5 M nitric acid aqueous solution, and the concentration of each metal ion was measured using an inductively coupled plasma mass spectrometer (ICP-MS).
4) For each metal ion, the concentration remaining in the aqueous phase was subtracted from the initial concentration to obtain the concentration extracted in the organic phase, and the extraction rate (= concentration in the organic phase / initial concentration) was determined.
図４は、上記のようにして求めた模擬廃液中のそれぞれの金属イオンの抽出率を示した図である。金イオンでは94％の抽出率が得られたが、金イオン以外の金属イオンは9％以下の抽出率であり、金イオンが高選択的に抽出されていることがわかる。また、この図から、化学的性質が類似していて金イオンとの分離が困難と言われる白金イオンやパラジウムイオンとも、十分に分離できていることがわかる。
（比較例１）
テトラアルキルアンモニウム塩を用いた模擬廃液からの金イオンの抽出
FIG. 4 is a diagram showing the extraction rate of each metal ion in the simulated waste liquid obtained as described above. An extraction rate of 94% was obtained with gold ions, but metal ions other than gold ions had an extraction rate of 9% or less, indicating that gold ions were extracted with high selectivity. In addition, this figure shows that platinum ions and palladium ions, which have similar chemical properties and are difficult to separate from gold ions, can be sufficiently separated.
(Comparative Example 1)
Extraction of gold ions from simulated wastewater using tetraalkylammonium salts
従来法であるBrust法では、液-液抽出過程において、テトラアルキルアンモニウム塩を用いて金イオンをトルエン相（抽出溶媒相）に抽出した後、抽出した金イオンをナノ粒子化する。そこで、（実施例１）と同じ模擬廃液を用いて金イオンの抽出を行い、（実施例１）の結果と比較した。
1）10 mMテトラオクチルアンモニウム（TOA）ブロマイドを含むトルエン溶液5 mlと（実施例1）と同じ模擬廃液5 mlを試験管の中に入れ、ボルテックスミキサーにより、15分間振とうした。
2）5分間の遠心分離の後、水相の一部を採取した。
3）採取した水相を0.5 M硝酸水溶液で希釈し、誘導結合プラズマ質量分析装置（ICP-MS）を用いて、それぞれの金属イオンの濃度を測定した。
4）それぞれの金属イオンについて、（実施例1）と同様にして抽出率を求めた。
In the conventional Brust method, gold ions are extracted into a toluene phase (extraction solvent phase) using a tetraalkylammonium salt in a liquid-liquid extraction process, and then the extracted gold ions are converted into nanoparticles. Therefore, gold ions were extracted using the same simulated waste liquid as in (Example 1) and compared with the results in (Example 1).
1) 5 ml of a toluene solution containing 10 mM tetraoctylammonium (TOA) bromide and 5 ml of the same simulated waste liquid as in Example 1 were placed in a test tube and shaken for 15 minutes with a vortex mixer.
2) After centrifugation for 5 minutes, a part of the aqueous phase was collected.
3) The collected aqueous phase was diluted with a 0.5 M nitric acid aqueous solution, and the concentration of each metal ion was measured using an inductively coupled plasma mass spectrometer (ICP-MS).
4) The extraction rate was determined for each metal ion in the same manner as in (Example 1).
図５は、上記のようにして求めた模擬廃液中のそれぞれの金属イオンの抽出率を示した図である。この図から、従来の製造方法では、金イオン以外にも多くの金属イオンが同時に抽出されてしまうことがわかる。
（実施例2）
AOT-TODGA逆ミセルに抽出した金イオンのナノ粒子化
FIG. 5 is a diagram showing the extraction rate of each metal ion in the simulated waste liquid obtained as described above. From this figure, it can be seen that in the conventional manufacturing method, many metal ions are simultaneously extracted in addition to gold ions.
(Example 2)
Nanoparticles of gold ions extracted into AOT-TODGA reverse micelles
金イオンを抽出したAOT-TODGA逆ミセルに還元剤を作用させて、金ナノ粒子を製造した。実験操作は以下の通りである。
1）金イオンを抽出したAOT-TODGA逆ミセルを含むイソオクタン溶液を4 ml分取し、ヒドラジンを2 mg添加した。
2）その後、ドデカンチオールを0.8 mg添加した。
3）イソオクタンをエバポレータで蒸発させ、残った金ナノ粒子をエタノールで洗浄した後、透過型電子顕微鏡を用いて観測した。
Gold nanoparticles were produced by applying a reducing agent to AOT-TODGA reverse micelles extracted with gold ions. The experimental procedure is as follows.
1) 4 ml of an isooctane solution containing AOT-TODGA reverse micelles extracted with gold ions was collected, and 2 mg of hydrazine was added.
2) Thereafter, 0.8 mg of dodecanethiol was added.
3) After isooctane was evaporated with an evaporator, the remaining gold nanoparticles were washed with ethanol, and then observed with a transmission electron microscope.
図６は、上記のようにして得られた金ナノ粒子の透過型電子顕微鏡写真である。個々の金ナノ粒子の表面はドデカンチオールによって化学修飾されていると考えられる。なお、金ナノ粒子の直径は、およそ5 nmである（表面修飾部分を除いて）。また、特性X線および電子線回折の測定結果から、ナノ粒子は高純度の金を成分としていることがわかった。 FIG. 6 is a transmission electron micrograph of the gold nanoparticles obtained as described above. The surface of each gold nanoparticle is considered to be chemically modified with dodecanethiol. The diameter of the gold nanoparticle is approximately 5 nm (excluding the surface modification portion). In addition, from the measurement results of characteristic X-rays and electron diffraction, it was found that the nanoparticles were composed of high-purity gold.
本発明に係る逆ミセル液-液抽出法は、例えば工場廃水を処理して金属含有ナノ材料を製造するなど、エコテクノロジーとナノテクノロジーの合わせ技として、また従来法よりも安全かつ簡便な方法として、種々の産業で利用できる。例えば、工業廃水処理技術としての利用が期待できる。現在、工業廃水中の金属の除去にはアルカリ沈殿法が用いられているが、この方法は簡便である反面、大量のアルカリを加えることによって生じるスラッジの問題を抱えている。廃水処理によって生じる莫大な量のスラッジは産業廃棄物として処分されるが、近年の産廃処分場の不足や処分場周辺の環境への影響が懸念され、大きな社会問題になっている。このような大きな環境負荷に加えて、廃水中の有価成分を廃棄物にしてしまっていることは、資源循環の考え方にも相反する。本発明によれば、産業廃棄物であるスラッジの代わりに価値の高い金属ナノ粒子が得られることで、環境負荷の大幅な軽減と同時に資源回収が可能となり、画期的な廃水処理法として利用可能である。 The reverse micelle liquid-liquid extraction method according to the present invention is a combined technique of ecotechnology and nanotechnology, such as processing factory wastewater to produce metal-containing nanomaterials, and as a safer and simpler method than conventional methods. Can be used in various industries. For example, utilization as industrial wastewater treatment technology can be expected. Currently, an alkali precipitation method is used to remove metals in industrial wastewater, but this method is simple but has a problem of sludge caused by adding a large amount of alkali. The enormous amount of sludge generated by wastewater treatment is disposed of as industrial waste. However, due to the recent shortage of industrial waste disposal sites and the impact on the environment around the disposal sites, it has become a major social problem. In addition to such a large environmental load, the fact that valuable components in wastewater are turned into waste also contradicts the concept of resource recycling. According to the present invention, high-value metal nanoparticles can be obtained in place of sludge, which is an industrial waste, so that it is possible to recover resources at the same time as drastically reducing the environmental burden, and it can be used as an innovative wastewater treatment method. Is possible.
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