Selective Extraction Of Metals From Chloride Solutions .

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Transcription Extraction of Metals from Chloride Solutions with theTetraoctylphosphonium Oleate Ionic LiquidDries Parmentier, ,‡,† Tom Vander Hoogerstraete,§,† Sybrand J. Metz, Koen Binnemans,§and Maaike C. Kroon*,‡ Wetsus, Centre of Excellence for Sustainable Water Technology, Oostergoweg 7, 8911 MA Leeuwarden, The NetherlandsSeparation Technology Group, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, DenDolech 2, 5612 AZ Eindhoven, The Netherlands§Molecular Design and Synthesis, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, box 2404, 3001 Heverlee, Belgium‡S Supporting Information*ABSTRACT: The solvent extraction behavior of a series of metal ions (Li , Na , K , Mg2 , Ca2 , Mn2 , Fe3 , Co2 , Ni2 , Cu2 ,Zn2 , In3 , La3 , Nd3 , Sm3 , Dy3 , Er3 , Yb3 ) from an aqueous chloride feed solution by the nonfluorinated fatty acid-based ionicliquid (IL) tetraoctylphosphonium oleate [P8888][oleate] has been investigated as a function of the pH. The possibility to extractmetal chlorides from an aqueous stream via the anion or cation of the hydrophobic, low-viscous water-saturated [P8888][oleate]IL has been exploited. [P8888][oleate] can be considered as a bifunctional or binary IL. At high pH values (pH 5), all metals areextracted via the oleate anion, whereas some transition metals are extracted at high HCl concentrations and thus low pH values asanionic chloro complexes in combination with [P8888] cations. A difference of one pH unit is observed between the extractioncurves (%E as a function of the pH) of the transition metals and those of the rare earth metals. Rare earths are not extracted atlow pH values, whereas some transition metals (Fe, Mn, Co, Zn, Cu, In) are extracted. This makes [P8888][oleate] a promisingextractant for the separation of transition metals from rare earths. It is also shown that this bulky and long-chained IL has a verylow viscosity due to the uptake of water. diminish the extraction efficiency.9 Other hydrophobic and lowviscous ILs are often prepared by using fluorinated anions suchas hexafluorophosphate (PF6 ) or bis(trifluoromethylsulfonyl)imide (Tf2N ). Besides the instability of the PF6 anion towardhydrolysis,5a fluorinated anions also have a high persistency innature. All these properties make fluorine-based ILs not as“green” as first assumed.Functionalized ionic liquids (FILs) are ILs that have aspecific functionality built into their structure. This is a metalbinding functional group in metal extraction systems.10 In thesearch for biocompatible, nontoxic FILs, we recentlysynthesized several nonfluorinated fatty acid-based ILs. Longchained tetraalkylphosphonium or tetraalkylammonium entitieswere selected as cations. These hydrophobic ILs have beenapplied for the extraction of several transition metals andshowed excellent extraction efficiencies.11 The bulky andhydrophobic cations prevent loss of the IL to the waterphase. Another advantage of the fatty acid-based ILs is that theanion of the IL is not lost during acidic stripping andregeneration, because protonation of the oleate anion to oleicacid does not alter the immiscibility with water. The conjugatedacids of some IL anions, such as in phthalate12 and βdiketonates,10c,13 are (partly) water miscible or volatile whichlimits the reuse of these ILs.INTRODUCTIONAlthough metals are essential for our economy, their supply isoften at risk. Therefore, the metallurgical industry is more andmore focusing on the recycling of metals.1 Separation andpurification of metal ions is often performed by liquid liquidextraction (solvent extraction).2 In this process, the metal isextracted from an aqueous phase by a hydrophobic organicextractant. However, conventional liquid liquid extractionsystems make use of organic solvents, which are often toxicand flammable. Ionic liquids (ILs) are proposed as a substituentfor volatile organic solvents.3 ILs are composed of organiccations and

Copper(II) chloride dihydrate, manganese(II) chloride dihy-drate, nickel(II) chloride hexahydrate, iron(III) chloride tetrahydrate, lithium chloride, and sodium chloride were supplied by Boom BV. Dysprosium(III) chloride, zinc(II) chloride, cobalt chloride hexahydrate, indium(III) chloride, and magnesium chloride were supplied by Sigma-Aldrich .

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