Separation and Purication Technology 80 (2011) 390395

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Separation and Purication Technology

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Liquidliquid extraction of transition metal ions with an alkylhistidine extractant

Hirofumi Morizono, Tatsuya Oshima , Yoshinari Baba
Department of Applied Chemistry, Faculty of Engineering, University of Miyazaki, 1-1, Gakuen Kibanadai Nishi, Miyazaki 889-2192, Japan

a r t i c l e

i n f o

a b s t r a c t
Liquidliquid extraction of transition metal ions using an alkylhistidine (histidine-2-ethylhexyl amide, abbreviated as His-EH) as a new extractant was studied. Intermediate metal cations in the Hard and Soft Acids and Bases (HSAB) sense, such as Cu(II), Ni(II), Zn(II) and Co(II), were selectively extracted with HisEH in the presence of other metal cations. The order of extractability for divalent transition metal ions was Cu(II) ) Ni(II) > Zn(II) > Co(II) % Cd(II) > Mn(II), which is approximately the order of the stability constants for complexes of histidine and the metal ions. From the results of slope analysis for Co(II) extraction, the complex stoichiometry was found to be 2:1 for His-EH and Co(II). In addition, the ion-pair extraction reaction of Co(II) with His-EH was in accordance with the equation: Co2 2His-EHorg aq 2ClO4aq Co2 His-EH2 ClO4 2org . The extraction equilibrium constant (Kex) of Co(II) using His-EH was evaluated as 3.03 1010 [(mol dm3)4]. 2011 Elsevier B.V. All rights reserved.

Article history: Received 22 December 2010 Received in revised form 19 May 2011 Accepted 23 May 2011 Available online 30 May 2011 Keywords: Liquidliquid extraction Histidine Transition metal ion Separation Extraction equilibrium constant

1. Introduction Liquidliquid extraction is one of the most promising techniques for separation of base metals, and such extraction processes have recently attracted attention for selective recovery of metal ions from industrial wastes. The extraction selectivity for the targeted metal using a specic extractant determines the success of the recovery process. A large number of extractants have been developed for separation of transition metal ions, including phosphoric acid, a-hydroxy oximes, b-diketones, amines and substituted pyridines, all of which are efcient for extraction [17]. Alkylimidazole has also been found to be an attractive candidate for extraction of base metal ions. Lenarcik et al. developed various alkylimidazole extractants for extraction of transition metal ions [811]. The nitrogen in the imidazole group is expected to exhibit afnity for divalent metal ions such as Cu(II), Ni(II), Co(II) and Zn(II) [12], on the basis of the afnity between the intermediate acid and the intermediate base according to Pearsons Hard and Soft Acids and Bases (HSAB) principle [13]. The stability constants of complexes of alkylimidazole extractants with Cu(II), Ni(II), Co(II) and Zn(II) have been determined. The partition constants of the complexes between metal ions and alkylimidazole extractants increased with increased alkyl chain length. The effect of bulkiness of the alkyl chains in the alkylimidazole extractants on the extraction of metal ions has also been studied in detail. Extractants bearing an imidazole group were found to be effective for the extraction of intermediate transition metal ions.
Corresponding author. Tel.: +81 985 58 7321; fax: +81 985 58 7323.
E-mail address: oshimat@cc.miyazaki-u.ac.jp (T. Oshima). 1383-5866/$ - see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.seppur.2011.05.026

In the present study, the alkylhistidine extractant histidine-2ethylhexyl amide (abbreviated as His-EH, shown in Fig. 1) was prepared as a new extractant for metal ions. The amino acid histidine is known to act as a metal chelator, especially for the intermediate metal ions Cu(II), Ni(II), Co(II) and Zn(II) [1416]. The alkyl histidine extractant has an imidazole group and an amino group, both of which could act as coordinating sites for intermediate metal ions. An imidazole-free extractant alanine-2-ethylhexylamide (abbreviated as Ala-EH, shown in Fig. 1) was also prepared as a structural analog for His-EH. The extraction efciencies of His-EH and Ala-EH for Co(II) were compared, to evaluate the effect of the imidazole group on metal extraction. Extraction of various metal ions was conducted to study the extraction selectivity of HisEH. As His-EH is a basic chelating extractant, a cobalt cation should be extracted into an organic phase with His-EH by an ion-pair extraction mechanism, with accompanying counter-anions. Hence the stoichiometry of the complex between His-EH and Co(II) in the presence of perchlorate ion was determined by slope analysis. Selective extraction of Co(II) and Cu(II) over other metal ions using His-EH was also considered from the viewpoint of possibility for practical usage of this extractant. In addition, back-extraction of Co(II) after extraction with His-EH was examined. 2. Experimental section 2.1. Apparatus Infrared spectra of the extractants His-EH and Ala-EH prepared in this study were obtained with a Fourier transform infrared spectrometer (JASCO, Co., FT-IR 4200, Tokyo, Japan). 1H NMR (400 MHz) spectra of the extractants in CDCl3 were recorded with a nuclear

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391

O Boc HN CH C OH + R NH2 O H Boc HN CH C N DMF R O H H2N NaOH CH C N R

EDC, HOBt

HCl/DXN

Fig. 1. Molecular structures of extractants used in this study.

His-EH: R = Ala-EH: R =

CH2 N CH3

NH

magnetic resonance spectrometer model AV400 M (Bruker Co., Rheinstetten, Germany). The pH of aqueous solutions was measured using a pH meter (HM-30S, DKK-TOA Co., Tokyo, Japan). A ame atomic absorption spectrophotometer (FAAS) model Analyst 100 (Perkin-Elmer Co., CT, USA) was used for determination of metal concentrations using an air-acetylene ame. 2.2. Materials and reagents Analytical grade copper(II), nickel(II), cobalt(II), zinc(II), manganese (II), cadmium(II), iron(III) and lithium(I) chlorides (Wako Pure Chemical Ind. Ltd.) were used to prepare test solutions of the metal ions. Analytical grade sodium perchlorate was used to control the perchlorate concentration. N-[(tert-butoxy)carbonyl]-histidine (Boc-His), N-[(tert-butoxy)carbonyl]-alanine (Boc-Ala), and 2ethylhexylamine (Tokyo Kasei Kogyo Co.) were used as raw materials to prepare extractants. All other reagents and solvents were of analytical grade or higher and were used as received. 2.3. Synthesis of histidine-2-ethylhexyl-amide (His-EH)

Fig. 2. Synthetic scheme for His-EH and Ala-EH.

addition of 4 M aqueous sodium hydroxide to adjust the pH to 8, the organic solvent was removed in vacuo, and a chloroform solution of the residue was washed with distilled water, then dried over anhydrous magnesium sulfate. After decantation, the chloroform was evaporated in vacuo. The following properties of the nal product (His-EH) were observed: FT-IR (KBr) mC@O 1656 cm1, mC@O 1706 cm1, mC@N 935 cm1; 1H NMR (400 MHz, CDCl3, 25 C) 0.87 (6H, m, CCH3), 1.23 (9H, m, CCH2C, CH(CH2)3), 3.02 (2H, d, ImCH2C), 3.16 (2H, m, CH2NH), 3.62 (1H, t, NHCHCO), 6.85 (1H, s, CONH), 7.56 (2H, s, Im). Ala-EH was synthesized in similar manner to His-EH by condensation reaction of N-[(tert-butoxy)carbonyl]-alanine (Boc-Ala) and

0.8

The synthetic scheme for the alkylated amino acids His-EH and Ala-EH that were used as extractants in this study is shown in Fig. 2. His-EH was synthesized by condensation reaction of N[(tert-butoxy)carbonyl]-histidine (Boc-His) and 2-ethylhexylamine (2-EHA), followed by removal of the Boc protecting group, as follows. To 150 cm3 DMF were added Boc-His (25.0 g, 97.9 mmol) and 2-EHA (12.7 g, 97.9 mmol). 1-hydroxybenzotriazole hydrate (HOBt, 14.6 g, 107.7 mmol) and 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDCHCl, 20.6 g, 107.7 mmol) were added, and the mixture was stirred for 24 h at 25 C. After evaporation in vacuo of DMF, a chloroform solution of the residue was washed with distilled water to remove residual Boc-His, EDC and HOBt, and dried over anhydrous magnesium sulfate. After decantation, the chloroform was evaporated in vacuo. The following properties of the resulting product (the intermediate Bochistidine-2-ethylhexyl-amide (Boc-His-EH)) were observed: FT-IR, (KBr) mC@O 1649 cm1, mC@O 1689 cm1, mC@N 937 cm1; 1H NMR (400 MHz, CDCl3, 25 C) 0.86 (6H, m, CCH3), 1.23 (9H, m, C CH2C, CH(CH2)3), 1.41 (9H, s, C(CH3)3), 3.10 (2H, d, ImCH2 C), 3.28 (2H, t, CH2NH), 4.44 (1H, m, NHCHCO), 5.88 (1H, s(br), Boc-NH), 6.87 (1H, s, CONH), 7.65 (2H, s, Im). The Boc group of Boc-His-EH was removed to obtain His-EH. To 50 cm3 of 4 M HCl in dioxane were added 28.6 g (78.3 mmol) of EH-Boc-His, and the mixture was stirred in an ice bath for 5 h. After

0.4

logD
0 -0.4 0 5 10 15 20 25 30 35

time [h]
Fig. 3. Effect of contact time on the distribution ratio of Co(II). [His-EH] = 6 mM, [Co(II)]ini = 0.1 mM, pHini = 6.0.

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2-EHA, followed by removal of the Boc protecting group using 4 M HCl in dioxane. The following properties the intermediate Boc-alanine-2-ethylhexylamide (Boc-Ala-EH) were observed: FT-IR, (KBr) mC@O 1655 cm1; 1H NMR (400 MHz, CDCl3, 25 C) 0.86 (6H, m, C CH3), 1.24 (9H, m, CCH2C, CH(CH2)3), 1.31 (3H, d, NHCH CH3), 1.41 (9H, s, C(CH3)3), 3.18 (2H, t, CH2NH), 4.13 (1H, m, NHCHCO), 5.14 (1H, d, Boc-NH), 6.32 (1H, s, CONH). The following properties of the nal product Ala-EH were observed: FT-IR (KBr) mC@O 1651 cm1; 1H NMR (400 MHz, CDCl3, 25 C) 0.88 (6H, t, CCH3), 1.28 (9H, m, CCH2C, CH(CH2)3), 1.47 (3H, m, NHCH CH3), 3.17 (2H, m, CH2NH), 3.48 (1H, q, NHCHCO), 7.40 (1H, s, CONH). 2.4. Liquidliquid extraction tests An aqueous solution was prepared by dissolving 0.1 mM metal ions Cu(II), Ni(II), Co(II), Zn(II), Mn(II), Cd(II), Fe(III) or Li(I) in 100 mM HEPES (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid) buffer solution. The pH was adjusted with a small amount of concentrated HCl or NaOH. An extracting solution was prepared by dissolving 10 mM extractant in chloroform. Equal volumes (10 cm3) of aqueous solution and the extracting solution were mixed in a 50 cm3 conical ask and mechanically shaken at 30 C for 24 h. After phase separation, the pH of the aqueous solution was measured using a pH meter, and metal ion concentrations in the aqueous solutions were determined by FAAS. The metal ion concentrations in the organic phases were calculated from the mass balance between the aqueous and organic phases. The extraction percentage (E%) and distribution ratio (D) of the metal were calculated from Eqs. (1) and (2), respectively.

to compare their extraction efcacies (Fig. 1). Fig. 4 shows that Co(II) was extracted with the commercial acidic extractants D2EHPA and PC-88A under weakly acidic conditions. Co(II) was also extracted with the basic extractant His-EH under weakly acidic conditions, and was quantitatively extracted at pH > 7. The efcacy of His-EH as an extractant for intermediate transition metals was comparable with that of commercial acidic extractants. By contrast, the percentage extraction of Co(II) with the basic extractant Ala-EH was quite small compared with that with His-EH. AlaEH has a primary amino group but does not have an imidazole group; thus the imidazole group of His-EH takes part in the extraction of Co(II). Fig. 5 shows the extraction behavior of various metal cations with His-EH as a function of pH. The divalent transition metal ions Cu(II), Ni(II), Co(II) and Zn(II), which are classied as intermediate acids according to the HSAB principle, were effectively extracted using the alkylated histidine extractant. The extraction of some metals such as Ni(II) and Zn(II) under neutral and weakly basic conditions could not be examined, due to the formation of precipitation. The order of extractability for divalent transition metal ions at pH 3.7 was Cu(II) ) Ni(II) > Zn(II) % Co(II) % Cd(II) > Mn(II), which is approximately in accordance with the order of the stability constants for complexes of the metal ions with histidine: Cu(II) (log K = [ML]/[M][L] = 10.2) > Ni(II) (log K = 8.67) > Co(II) (log K = 6.90) > Zn(II) (log K = 6.55) > Cd(II) (log K = 5.39) > Mn(II) (log K = 3.30) [17].

3.2. Determination of complex species The complexation mechanism between Co(II) and His-EH was investigated by slope analysis. Fig. 6 shows the effect of His-EH concentration on the extraction of Co(II). The logarithm of the distribution ratio increased with increasing concentration of His-EH. The slope of the relationship between the logarithm of the distribution ratio of Co(II) and the logarithm of the His-EH concentration was 2, which indicates that two His-EH molecules are involved in the extraction of a cobalt ion. The stoichiometry is similar to that for alkylimidazole extractants and Co(II) [811].

Morg;eq Maq;init Maq;eq E% 100 100 Maq;init Maq;init D Morg;eq Maq;init Maq;eq Maq;eq Maq;eq

Extraction [%]

where [M]aq,init represents the initial concentration of metal ion in the aqueous phase. [M]aq,eq and [M]org,eq are the total concentrations of metal ion in the aqueous and organic phases, respectively, at equilibrium. Moreover, the complexation mechanism between Co(II) and His-EH was investigated by slope analysis. Effect of the His-EH concentration on the distribution ratio (D) of Co(II) was investigated at pH 6.0. Similarly, the effect of perchlorate ion concentration (30 300 mM) on the distribution ratio (D) of Co(II) was investigated at pH 4.4. The concentration of perchlorate ion was controlled using sodium perchlorate in the aqueous phase. 3. Results and discussion 3.1. Extraction equilibrium of metal ions with histidine extractants As intermediate metal ions such as Cu(II), Ni(II), Co(II) and Zn(II) form stable complexes with histidine, extraction of Co(II) using His-EH was examined as a model case. The effect of contact time on the extraction of Co(II) with His-EH was studied to determine the time required for attainment of extraction equilibrium. Fig. 3 shows the time course of Co(II) extraction with His-EH (6 mM) at 30 C. The logarithm of the distribution ratio increased with time and approached a constant value at 24 h. Hence the extraction experiments were conducted by maintaining contact between aqueous and organic phases for 24 h. Extraction of Co(II) using different extractants, namely His-EH, Ala-EH, D2EHPA and PC-88A, was carried out as a function of pH

100

His-EH
80

D2EHPA PC-88A

60

Ala-EH
40

20

0 0 2 4 6 8 10

pHeq
Fig. 4. Effect of equilibrium pH on the extraction of Co(II). [Extractant] = 10 mM, [Co(II)]ini = 0.1 mM.

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393

100

Cu(II)
80

Ni(II) Co(II)
2

Extraction [%]

60

Zn(II)

40

logD

Cd(II) Mn(II)

20

Fe(III) Li(I)
0

0 0 2 4 6 8 10

pHeq
Fig. 5. Effect of equilibrium pH on the extraction of metal ions using His-EH. [HisEH] = 10 mM, [metal]ini = 0.1 mM.

-1 -2 -1.5 -1

1
-0.5 0

log[ClO4-]
2.5
Fig. 7. Effect of perchlorate ion concentration on the distribution ratio of Co(II) with His-EH. pHini=4.4, [His-EH]=0.5 mM, ClO4 ini = 30300 mM, [Co(II)]ini = 0.1 mM.

1.5

extraction was omitted in the following determination of extraction reaction for Co(II), to simplify the equation. From the results of slope analysis, the extraction reaction of Co(II) with His-EH can be represented by Eq. (3):

logD

Co2 2RN 2ClO4 Co2 RN2 ClO4 2

0.5

The bar denotes the species in the organic phase, and RN denotes His-EH. The extraction equilibrium constant Kex is given by Eq. (4)

2
-0.5

K ex

Co2 RN2 ClO4 2 Co2 RN2 ClO4 2

and the distribution ratio of Co(II) between the organic and aqueous phases is dened as

1
-1.5 -4 -3 -2 -1 0

Co2 org;eq Co2 aq;eq

Co2 RN2 ClO4 2 Co2

log[RN]
Fig. 6. Effect of extractant (His-EH = RN) concentration on the distribution ratio of Co(II). pHini = 6.0, [His-EH]=0.55 mM, [ClO4-]ini=10 mM, [Co(II)]ini=0.1 mM.

By combining Eqs. (4) and (5), Eq. (6) in its logarithmic form can be obtained:

log D 2log RN 2log ClO4 log K ex

As His-EH is a basic chelate extractant, cobalt cations should be extracted into an organic phase with His-EH by an ion-pair extraction mechanism, with accompanying counter-anions. The effect of the perchlorate ion ClO4 concentration on the extraction of Co(II) with His-EH was examined, because perchlorate ion is usually preferred as a counter-anion to other anions on the basis of the Hofmeister series [1821]. The loglog plot in Fig. 7 shows the effect of perchlorate ion concentration on the distribution of Co(II) using His-EH at pH 4.5. The logarithm of the distribution ratio increased with increasing perchlorate ion, and the slope of the relationship between log D for Co(II) and the logarithm of the perchlorate ion ClO4 concentration is 2, which indicates that two perchlorate ions are involved in the extraction of Co(II). The extraction of proton using the basic extractant His-EH, which is competitive that of metal ions, is found to be occurred under weakly acidic, neutral, or basic condition. However, the proton

Eq. (6) means two His-EH molecules and two perchlorate ions are involved in the extraction of a cobalt ion, as shown in the results in Figs. 6 and 7. Eq. (6) can also be represented by Eq. (7):

log D log RN2 ClO4 2 log K ex

The experimental log D data for extractants are plotted in Fig. 8. The theoretical line based on Eq. (7) is in good agreement with the experimental results, indicating that the extraction equilibrium of Co(II) with the extractant is in accordance with Eq. (3). The extraction equilibrium constant (Kex) of Co(II) using His-EH was evaluated from the intercept of the straight line with the ordinate of Fig. 8 as 3.03 1010 [(mol dm3)4]. 3.3. Selective extraction of divalent metal cations On the basis of the results presented in Fig. 5, selective extraction of divalent metal ions over other metals is achievable using

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2.5

1.5

0.5

-0.5

[RN] [ClO4-] theoretical line

Separation of copper from iron is important in liquidliquid extraction processing. Hydroxyoxime extractants such as the commercial extractant LIX 984 are well known for selective extraction of Cu(II) over Fe(III) in acidic media [24,25]. Selective extraction of Cu(II) in the presence of Fe(III) is also important from the viewpoint of recovery of base metals from electronic wastes such as waste printed circuit boards [26]. For that reason selective extraction of Cu(II) from excess Fe(III) using His-EH was examined, and Fig. 10 shows the results of extraction of Cu(II) from a Cu(II)/Fe(III) mixture at pH 2.0. Cu(II) was selectively extracted with His-EH even in the presence of a 30-fold excess of Fe(III). Thus the histidine extractant was found to be highly effective for selective extraction of Cu(II) from a Cu(II)/Fe(III) mixture under moderately acidic conditions. 3.4. Back extraction of metal ions extracted with His-EH A back-extraction test of Cu(II), Ni(II) and Co(II) extracted with His-EH was examined using an aqueous solution containing EDTA, aqueous acidic solutions, and mixed solutions containing hydrochloric acid and ascorbic acid. The results of the tests, summarized in Table 1, show that the chelating agent EDTA effectively stripped all Cu(II), most Ni(II) and some Co(II) from the organic phase. The order of back-extraction selectivity was Cu(II) > Ni(II) ) Co(II), which is in accordance with the order of the stability constants for EDTA complexes of the metal ions [16]. Back-extraction of Co(II) was not effective using acidic solutions, and Co(II) was not back-extracted at all under moderately acidic conditions. As Co(II) extracted with His-EH might be oxidized to Co(III), back-extraction of Co(II) was examined using 1.0 M aqueous hydrochloric acid, in the presence of ascorbic acid as a reductant to prevent oxidation of Co(II). The percentage back-extraction increased with increased ascorbic acid concentration, and 83% of Co(II) was stripped from the organic phase in the presence of 0.3 M ascorbic acid. Consequently, back-extraction of Co(II) should be carried out in a reducing environment. However, oxidation of Co(II) should be suppressed for the cycle use of the extraction phase.

logD

-1.5 -12

-10

-8

-6

log([ClO4-]2 [RN]2)
Fig. 8. The dependence of the distribution ratio of Co(II) using His-EH on His-EH concentration and perchlorate ion concentration; the solid line is the theoretical line.

His-EH, at controlled pH. Extraction of Co(II) and Cu(II) was carried out in the presence of excess coexisting metals. Lithium (1.41.9 wt.%) and cobalt (1216 wt.%) are contained in the lithium ion rechargeable batteries (LIBs) that are used for cellular telephones and laptop computers. A hydrometallurgical process for recovery of cobalt from waste cathode active material of lithium ion batteries has been reported [22,23]. In the present study, selective extraction of cobalt from lithium by an alternative route using His-EH was carried out. Fig. 9 shows the results of extraction of Co(II) from a Co(II)/Li(I) mixture at pH 7.0. Co(II) was selectively extracted with His-EH even after increasing the concentration of Li(I), thus separation of Co(II) from Li(I) can be realized using the histidine extractant and controlling pH.

100

50

40
80

Extraction [%]

Extraction [%]

60

Co Li

30

Cu Fe

40

20

20

10

0
0

10

20

30

40

10

20

30

40

[Li] / [Co]
Fig. 9. Selective extraction of Co(II) from a Co(II)/Li(I) mixed solution. pHini = 7.0, [NaCl] = 100 mM, [His-EH] = 10 mM, [Co(II)] = 1 mM, [Li(I)] = 130 mM.

[Fe] / [Cu]
Fig. 10. Selective extraction of Cu(II) from a Cu(II)/Fe(III) mixed solution. pHini = 2.0, [NaCl] = 100 mM, [His-EH] = 20 mM, [Cu(II)] = 1 mM, [Fe(III)] = 130 mM.

H. Morizono et al. / Separation and Purication Technology 80 (2011) 390395 Table 1 Back-extraction of metal ions extracted with His-EH into chloroform. [HisEH] = 10 mM, [metal]ini = 0.1 mM. Back-extraction reagent 0.1 M EDTA 0.1 M EDTA 0.1 M EDTA 0.1 M HCl 0.1 M HNO3 0.1 M H2SO4 1.0 M HCl 1 M HCl + 0.05 M ascorbic acid 1 M HCl + 0.10 M ascorbic acid 1 M HCl + 0.30 M ascorbic acid Metal Cu(II) Ni(II) Co(II) Co(II) Co(II) Co(II) Co(II) Co(II) Co(II) Co(II) Back-extraction (%) 96 82 48 35 31 35 13 47 50 83

395

4. Conclusions The newly prepared extractant His-EH (histidine-2-ethylhexylamide) was found to be efcient for extraction of transition metal ions with intermediate properties in relation to the HSAB concept. The efcacy of His-EH for extraction of intermediate transition metals was comparable with that of commercial acidic extractants. As the efcacy of His-EH was much higher than that of Ala-EH, the imidazole group is thought to be implicated in the extraction of metal ions. Intermediate metal cations such as Cu(II), Ni(II), Co(II) and Zn(II) were selectively extracted with His-EH on the basis of their afnity with histidine. The stoichiometry of the complex between His-EH and Co(II) in the liquidliquid extraction system was conrmed by the results of slope analysis. Co(II) was effectively stripped from the organic phase in the presence of 0.3 M ascorbic acid. The alkyl histidine extractant, which has an imidazole group and an amino group as coordinating sites, was established as an efcient extractant for intermediate metal ions. References
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