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Minerals 2021, 11, x Minerals 2022, 12, 190 3 of 13 3 of 12 in brines, considering an extracting phase composed of a synergistic agent and different thermodynamic model, the extraction stoichiometry of this metal with ILs and a neutral hydrophobic ILs as extractants diluted in conventional organic solvents. In this thermo- donor must be known, which could be summarized as follows. dynamic model, the extraction stoichiometry of this metal with ILs and a neutral donor must be known, whxic+h could be summarized as follows. + M(aq) + yN(org) + xCA(org) β MAX Ny(org) + xC(aq) (1) πτ°τ° τ°π¦π τ°π₯πΆπ΄ + (τ°τ°) (τ°τ°τ°) βππ΄π τ°π₯πΆτ° (τ°τ°τ°) τ° τ°(τ°τ°τ°) (τ°τ°) (1) extraction, the literature indicates that SX proceeds via cation exchange and ++ For Li solvatFionr mLiecehxatrnaicstmiosn[,1t2h,3e1l,i3te2r]a. tSuprecinfidcaiclalyt,efsotrheaatcShXmporloeceoefdlisthviiuamcaetxiotrnacetxecdh,aonngemanodle osfotlhveataionniomne(cAh)anoifsmthse[I1L2,3(C1,A32)]a.nSpdetcwifiocamllyo,lefosroefaachnmeuotlreaolfdliothniourm(Nex)tararectnedee, odneed.mTohlee + etry for different metals is obtained through Equation (2). Mx+Cln(aq) +2TBP(org) +xCA(org) β Mx+AxΒ·2TBP(org) +xCCl(aq) (2) πτ°τ°πΆπτ°(τ°τ°) τ° 2ππ΅π(τ°τ°τ°) τ° π₯πΆπ΄(τ°τ°τ°) β πτ°τ°π΄τ° β 2ππ΅π(τ°τ°τ°) τ° π₯πΆπΆπ(τ°τ°) (2) Noaf thceaatinoinonex(Ahi)boitfsthaelmILo(sCt Ath)eansadmtwe oiomnioclersaodfiiaanseulitrhailudmon[o33r ](;Na)saarecnoenesdeeqdu.eTnhce,Ntahe cocaotridonineaxtihoinbintsuamlmbeorstwthilelbsaemrelaiotendictroadthiisapsrliotphieurmty,[a3m3]o;ansgaoctohnersefqaucteonrcse[,3t4h]e.cInootrudrin,ai-n thtieonexnturamctbioernwstiollicbheioremlaetterdytoftmhiasgpnreospieurmty,(Mamgo)nwgitohthIeLrs,fatchtiosrms [e3t4a]l.iIonntuisrnc,oionrdthineaetxe-d wtritahcttiwonosatonicohnisomofeItLry[o20f ,m35a]gannedsiutwmo(Mmgo)lewciuthleIsLosf, tThBisPm[3e6ta].l iCoonnisicdoeorridnignathteisd, wa igthentewroal staoniicohniosmofeItLry[2f0o,r3d5]ifafenrdentwtmometaolsecisuloebstoafinTeBdPth[3r6o]u.gChonEsqidueartionngt(h2)i.s,ageneralstoichiom- x+ + + 2+ With M τ°τ° = Liτ° , Nτ°a , τ°Mτ° g and sub-indices aq and org corresponding to the With π = πΏπ , ππ , ππ and sub-indices aq and org corresponding to the aque- aqueous and organic phase, respectively. ous and organic phase, respectively. Figure 1 summarizes SX stoichiometry and the steps involved in the SX process, Figure 1 summarizes SX stoichiometry and the steps involved in the SX process, showing the path followed by the extractant IL (CA) when extracting metal ions (Mx+) wxi+th showing the path followed by the extractant IL (CA) when extracting metal ions (M ) a charge (x) from aqueous solutions. with a charge (x) from aqueous solutions. Figure 1. Proposed extraction path for the IL extractant and a neutral donor in the SX process of a Figure 1. Proposed extraction path for the IL extractant and a neutral donor in the SX process of a certain metal. certain metal. In Figure 1, the IL extractant, which is initially present in the organic medium In Figure 1, the IL extractant, which is initially present in the organic medium (CA(org)), (πΆπ΄(τ°τ°τ°)), is transferred to the aqueous phase according to its distribution constant (πΎτ°,τ°τ°). is transferred to the aqueous phase according to its distribution constant (KD,CA). Once Once there, it is solvated by water, dissociating to some extent into a+cation (πΆτ° ) and (τ°τ°) there, it is solvated by water, dissociating to some extent into a cation (C(aq)) and into an an- into an anion (π΄τ° ) according to their dissociation constant (πΎ ). The anion π΄τ° is re- β (τ°τ°) τ°τ° β (τ°τ°) ion (A(aq)) according to their dissociation constant (KCA). The anion A(aq) is responsible for sponsible for extracting the metals from an aqueous solution, displacing chloride ions extracting the metals from an aqueous solution, displacing chloride ions from lithium [37]. from lithium [37]. Additionally, the neutral donor is distributed between organic and the Additionally, the neutral donor is distributed between organic and the aqueous phases aqueous phases given by the distribution constant (πΎτ°,τ° ). given by the distribution constant (KD,N). τ°τ° Then, extraction is carried out, forming the π π΄τ°πτ° complex, for which its ex- x+ traction constant is defined by πΎτ°‘. Finally, the organometallic complex formed from the Then, extraction is carried out, forming the M extractionconstantisdefinedbyKf. Finally,theorganometalliccomplexformedfrom AxNy(aq) complex, for which its previous complexation dissolves into the organic phase according to the distribution con- the previous complexation dissolves into the organic phase according to the distribution stant (πΎ ) between the aqueous and organic phases. All these equilibrium constants and constantτ°(,Kτ° D,C) between the aqueous and organic phases. All these equilibrium constants distribution ratios are defined as follows by Equations (3)β(7). and distribution ratios are defined as follows by Equations (3)β(7). (τ°τ°) KD,CA = [CA](aq) (3) [CA](org)PDF Image | Ionic Liquids for the Selective Solvent Extraction of Lithium
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