Journal of Chemical Engineering of Japan, Vol. 44, No. 5, pp.

307–312, 2011 Research Paper

Application of Ionic Liquids to Extraction Separation of Rare Earth Metals

with an Effective Diglycol Amic Acid Extractant
Fukiko KUBOTA1, Yousuke SHIMOBORI1, Yuzo BABA1,
Yusuke KOYANAGI1, Kojiro SHIMOJO3, Noiho KAMIYA1,2
and Masahiro GOTO1,2
1
Department of Applied Chemistry,
Graduate School of Engineering, Kyushu University,
744, Motooka, Fukuoka-shi, Fukuoka 819-0395, Japan
2
Center for Future Chemistry, Kyushu University,
744, Motooka, Fukuoka-shi,Fukuoka 819-0395, Japan
3
Division of Environment and Radiation Science,
Nuclear Science and Energy Directions, Japan Atomic Energy Agency,
Tokai-mura, Ibaraki 319-1195, Japan

Keywords: Ionic Liquids, Rare Earth, Extraction, Separation, Metal Recycling

The application of ionic liquids as alternatives to conventional organic solvents in extraction processes has
been actively investigated. A crucial step towards the practical use of ionic liquids is the development of extrac-
tants that work effectively within these new media. In the present study, the extraction separation of rare earth
metals into ionic liquids, 1-butyl, 1-octyl, and 1-dodecyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide
([Cnmim][Tf2N], n  4, 8, 12), was performed using a novel extractant, N,N-dioctyldiglycol amic acid
(DODGAA). Quantitative extraction of metal ions such as Y3 and Eu3 was selectively achieved in the presence
of the base metal ion Zn2, which was not extracted at all under the present experimental conditions. The extrac-
tion efficiency was enhanced for the shorter-alkyl-chain imidazolium ionic liquid [C4mim][Tf2N] compared to
that for a conventional organic solvent system. Extraction mechanism studies elucidated that the metal extrac-
tion proceeds via proton exchange reactions between DODGAA and the metal ions in the ionic liquid (the same
mechanism as in the conventional organic solvent). The stripping reaction, or recovery, of the metal ions from the
extracting phase was readily accomplished with an acid solution such as nitric acid.

Seddon, 2008; Liu et al., 2009; Sun and Armstrong,

Introduction
2010). ILs, which are molten salts generally composed
Liquid–liquid extraction is now widely used in in- of organic cations and various anions, have unique prop-
dustrial and analytical fields for the separation and pu- erties such as high thermal stability, negligible vapor
rification of metal ions. However, in conventional sol- pressure, and nonflammability, and are thus regarded as
vent extraction, toxic and/or volatile diluents are com- eco-friendly solvents. Their greatest appeal is that their
monly employed. In recent years, industrial wastes and physicochemical properties such as polarity, viscosity,
scrap such as spent TV displays, fluorescent lamps, bat- density, and affinity with other solvents are extensively
teries, and cellular phones have been highlighted as tunable by varying the combination of cationic and an-
valuable secondary resources of rare metals. Therefore a ionic partners (Huddleston et al., 2001; Anderson et al.,
highly efficient separation technique for the recovery of 2002). Water immiscible ILs have a variety of potential
these metals from such potentially complex mixtures is applications in separation and analytical chemistry as
required (Nakamura et al., 2007; Kubota et al., 2009; Li separation media (Zhao et al., 2005; Kubota and Goto,
et al., 2009; Pranolo et al., 2010). 2006; Liu et al., 2009; Sun and Armstrong, 2010). Since
Growing attention has recently focused on room Dai et al. (1999) first reported that the use of ILs as ex-
temperature ionic liquids (ILs) as alternatives to conven- traction diluents for metal ions offered significant im-
tional organic solvents (Huddleston et al., 2001; provements in extraction efficiency, IL-based extraction
Anderson et al., 2002; Rogers and Seddon, 2002; Zhao systems for metal ions have been intensively investigated
et al., 2005; Kubota and Goto, 2006; Plechkova and using several conventional commercial extractants. The
use of dicyclohexano-18-crown-6 (DC18C6) as an ex-
tractant in imidazolium-based ILs significantly improves
Received on January 11, 2011; accepted on February 27, 2011 the extraction efficiency for Sr2 compared to that the
Correspondence concerning this article should be addressed to
F. Kubota (E-mail address: [email protected]).
use in a traditional organic solvent system. Enhancement

Copyright © 2011 The Society of Chemical Engineers, Japan 307

of the extractability of lanthanides and selectivity among
the metal ions with octyl(phenyl)-N,N-diisobutylcar-
bamoylmethyl phosphine oxide (CMPO) has also been
demonstrated in IL systems (Nakashima et al., 2003,
2005; Visser and Rogers, 2003). Although ILs have a
number of advantages as extracting solvents, there have
Fig. 1 Molecular structures of extractant DODGAA and imi-
been limitations to their practical use, imposed by the
dazolium-based ILs (Shimojo et al., 2007; Kubota et
difficulty in finding a suitable soluble extractant. While
al., 2010)
neutral extractants such as DC18C6 and CMPO are
readily soluble in ILs, their behavior in IL systems is dif-
ferent from that in organic solvents. This change causes
the loss of ILs to the aqueous phase and also compli- 1. Experimental
cates the recovery of the metal ions from the IL phase 1.1 Reagents
(Dietz and Dzielawa, 2001; Visser and Rogers, 2003; The extractant DODGAA shown in Figure 1 was
Nakashima et al., 2005). Extraction of metal ions with a synthesized from diglycolic anhydride and dioctylamine
typical chelating β -diketone such as thenoyltrifluoroace- as described previously (Naganawa et al., 2007; Shimojo
tone (HTTA) has also been associated with the release of et al., 2007). ILs—1-ethyl-, 1-butyl-, 1-octyl-, and 1-
IL constituents to the aqueous phase (Jensen et al., 2003; dodecyl-3-methylimidazolium bis(trifluoromethanesul-
Kidani et al., 2008), although such proton-exchange- fonyl)imide (abbreviated as [Cnmim][Tf2N], n  2, 4, 8,
type extractants enable effective stripping of the metal 12)—were synthesized as described previously (Kubota
ions from the ILs by controlling the pH value of the et al., 2008). The commercial extractant Versatic 10, a
aqueous phase. The proton exchange-type organophos- tertiary-branched carboxylic acid, was kindly supplied
phorus extractants, bis(2-ethylhexyl)phosphoric acid by Japan Epoxy Resin Co., Ltd. (now Mitsubishi
(D2EHPA) and 2-ethylhexylphosphonic acid mono-2- Chemical Co.). All other chemicals were of reagent
ethylhexyl ester (PC-88 A), show similar proton-ex- grade.
change equilibria for metal ions such as UO2, Am3, 1.2 Extraction procedure
and the rare earth metals in ILs as in conventional or- Extraction equilibrium studies were performed by
ganic solvents (Cocalia et al., 2005; Kubota et al., the conventional extraction method. Extracting phases
2008); however, previous researchers did not achieve were prepared by dissolving the extractant DODGAA in
high recovery of the metal ions due to their poor solubil- the ILs, or in n-dodecane containing 5 vol% 1-octanol as
ity in the ILs. Significant efforts have been devoted to a solubilizer (Shimojo et al., 2007). Aqueous solutions
develop a novel extractant suitable for ILs, enabling ILs containing 0.1 mol/m3 metal ions were prepared by
to be exploited for metal recovery (Luo et al., 2004; dissolving nitrate salts of Y3, Eu3 and Zn2 in
Shimojo and Goto, 2004; Shimojo et al., 2009). 100 mol/m3 nitric acid and 100 mol/m3 sodium acetate
Recently, we reported that an advanced liquid mem- solutions. The pH values of the aqueous solutions were
brane extraction system for rare earth metals using ILs adjusted by mixing these aqueous solutions in appropri-
could be developed by employing the newly synthesized ate ratios. Equal volumes (2 cm3) of the aqueous and or-
N,N-dioctyldiglycol amic acid (DODGAA) as an extrac- ganic solutions were mixed in a sealed glass tube and
tant (Kubota et al., 2010). The liquid membrane system gently shaken at 298 K to attain equilibrium. After phase
is the most feasible technology for the application of ex- separation, the concentrations of the metal ions in the
pensive ILs as extraction media because only a small aqueous phase were measured with an inductively cou-
amount of solvent is used within the membrane. pled plasma-atomic emission spectrometer (ICP-AES,
DODGAA, which is an anionic ligand having a car- Optima 5300, Perkin Elmer Co.). Stripping of the metal
bamoyl and a carboxyl group connected by an ether ions from the extracting phase using nitric acid solution
chain, can be prepared with relative ease from a com- was also examined. The extraction and stripping degrees
mercially available starting reagent (Naganawa et al., of the metal ions, E [—] and E [—] were calculated by
2007; Shimojo et al., 2007). In the present study, we in- the following equations:
vestigated the extraction behavior of rare earth metals E  ([M]aq,0  [M]aq) / [M]aq,0 (1)
with DODGAA in imidazolium-based ILs and eluci-
dated the extraction mechanism. The application of ILs E  [M]aq,strip / [M]IL,0 (2)
to the separation and recovery of rare earth metals (yt-
trium (Y) and europium (Eu)) from base metals such as
2. Results and Discussion
zinc (Zn) was examined as a model case for the recovery
of valuable metals. These metals are the main compo- 2.1 Extraction behavior of metal ions in ionic liquid
nents of the waste fluorescent materials in used TV tubes systems
(Kubota et al., 2001). The extraction behavior of metal ions (Y3, Eu3,
and Zn2) in ILs with DODGAA is shown in Figure 2

308 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

Fig. 2 Extraction behavior of metal ions with DODGAA
Fig. 3 Comparison of extractability and selectivity for metal
in IL and n-dodecane systems. [M]i  0.1 mol/m3,
ions between DODGAA and Versatic 10. [M]i 
[DODGAA] = 10 mol/m3; metal ions: Y3 (filled sym-
0.1 mol/m3, [Extractant]  10 mol/m3
bols), Eu3 (open symbols), Zn2 (gray symbols);
solvents: [C4mim] (circle), [C8mim] (diamond),
[C12mim] (square), n-dodecane (triangle)
liquids. Further detailed investigations are required.
Whereas quantitative extraction was achieved for
Y3 and Eu3 with DODGAA (as shown in Figure 2),
as a function of the equilibrium pH in the feed aqueous no Zn2 was extracted into any extraction phases under
phases. A control n-dodecane system is also shown. The the present experimental conditions. The high ex-
degree of extraction, E, for Y3 and Eu3 increased with tractability and selectivity for the rare earth metal ions
increasing pH in the IL systems as well as the n-dode- against Zn2 can be attributed to the putative tridentate
cane system. The results suggest that the metal extrac- diglycol amic acid frame because as shown in Figure 3,
tion into ILs proceeds via proton exchange from the ex- the extractabilities of Y3 and Eu3 were as low as that
tractants for the metal ions, similar to the n-dodecane of Zn2 when Versatic 10 was used. It was demonstrated
system. For the three ILs with different alkyl chain that the extractant DODGAA was useful for the recovery
lengths in the imidazolium cation, the extraction effi- of rare earth metals from the leaching solution of elec-
ciency for Y3 and Eu3 increased in the [C4mim]  tronic wastes such as fluorescent materials, even in the
[C8mim]  [C12mim] and was greatly enhanced in the presence of a large amount of base metal such as Zn2.
[C4mim][Tf2N] compared to that in the n-dodecane sys- A compound having a structure similar to
tem. Although DODGAA is a proton-dissociation-type DODGAA, N,N,N,N-tetra(n-octyl)-diglycolamide
extractant with a carboxyl group, it was readily soluble (TODGA) (which is a neutral tridentate ligand with two
in all the ILs tested, even in [C2mim][Tf2N]. This solu- carbamoyl groups connected by an ether chain), has also
bility was not observed for the proton-dissociation-type been reported to exhibit a high affinity for rare earth
extractants PC-88 A and D2EHPA. Moreover, the metal metals (Shimojo et al., 2008). Since the proton of
ions were effectively stripped in a manner identical to DODGAA cannot dissociate in highly acidic conditions,
that in the case of the organic solvent system. The high DODGAA may react as a neutral tridentate extractant
solubility of DODGAA in polar ILs was assumed to be like TODGA for metal ions in the aqueous phase at high
due to the polar nature of the oxygen-containing core of acid concentrations. Thus, the extraction behavior of
the molecule. The related alkyl monocarboxylic acid, DODGAA was also examined for a high nitric acid con-
Versatic 10, was less soluble in ILs. The solubility of centration range in the aqueous phase. At nitric acid con-
DODGAA was higher in ILs with longer imidazolium centrations between 0.5 mol/dm3 and 5 mol/dm3, Y3 and
cation alkyl substituents, similar to what has been ob- Eu3 were not extracted as well as Zn2 into either the
served for PC-88A (Kubota et al., 2008) and Versatic 10. organic solvent or the IL systems.
A precipitate, perhaps the insoluble DODGAA-metal Figure 4 shows the stripping behavior of Y3 and
3
complex, appeared at the water-IL interface at equilib- Eu from [C4mim][Tf2N] to nitric acid solutions. The
rium in the [C2mim][Tf2N] system. The extraction abil- metal ions were readily stripped with nitric acid and
ity of the solvents mentioned above was considered to quantitative recovery was achieved at concentrations of
depend on the partitioning property of the extractant in nitric acid above 0.5 mol/dm3. On the basis of the results
the aqueous and organic phases and the solubility of the of extraction and stripping experiments, it was con-
extracted metal complex. The extraction ability may also firmed that DODGAA was an acidic extractant and that
be to the result of a peculiar solvent effect of the ionic it extracted the metal ions exclusively via a proton ex-

VOL. 44 NO. 5 2011 309

Fig. 4 Stripping behavior of metal ions from IL phase
([C4mim][Tf2N]) with nitric acid. [M]IL,0  0.1
Fig. 5 Slope analysis for extraction of rare earth metals. (a)
mol/m3, [DODGAA]IL  10 mol/m3
log D versus pH. (b) log D versus DODGAA concen-
tration [HR]. Metal ions: Y3 (filled symbols), Eu3
(open symbols), solvents: [C4mim] (circle), [C8mim]
change mechanism, maintaining the mass balance of (diamond), [C12mim] (square), n-dodecane (triangle);
metal ions between the aqueous and IL phases. [M]i  0.1 mol/m3. (a) [DODGAA]  10 mol/m3, (b)
2.2 Extraction mechanism of rare earth metal ions pH: 1.2 ([C4mim]), 1.8 ([C8mim]), 1 (n-dodecane)
with DODGAA
In the IL system, neutral extractants such as
CMPO, DC18C6, and also TODGA are known to extract
metal ions by a mechanism different from that occurring
in organic solvents (Dietz and Dzielawa, 2001;
Nakashima et al., 2005; Shimojo et al., 2008). That is,
metal ions are extracted into ILs without the co-extrac-
tion of counterions such as nitrate, from the aqueous
phase. Instead, the imidazolium cations are released
to the aqueous phase, as demonstrated by a decrease in
the extractability of metal ions with increasing con-
centration of C4mim doped into the aqueous phase
(Nakashima et al., 2005). In the present study with
DODGAA, the extraction performance for Y3 and Eu3
was not affected by the addition of C4mim to the aque-
ous feed phase, indicating that metal transfer with
DODGAA into ILs does not involve C4mim exchange.
Slope analysis of the distribution ratio D
( [M]ext / [M]aq) was performed as a function of the
equilibrium pH and concentration of DODGAA. As Fig. 6 Loading test for Y3 on DODGAA in [C8mim][Tf2N].
shown in Figure 5(a), straight lines with slope 3 were [DODGAA]  6 mol/m3, pH  5.2
obtained from the plots of log D against pH for the IL
system as well as for the n-dodecane system. Therefore,
three protons were released to the aqueous phase for the M3  3(HR)2,org  MR33HRorg  3H (4)
extraction of one metal ion. The plots of log D versus log
[DODGAA] also gave straight lines with a slope of 3 for A linear dependency of slope 3 should also be obtained
both systems, as shown in Figure 5(b). These results for the log plots of D versus the concentration of the ex-
suggest that the extraction equilibrium equation for Y3 tractant dimer when the metal ion forms a 1 : 3 complex
and Eu3 with DODGAA (HR) is as follows: with the dimers. It seems to be difficult for DODGAA to
dimerize in polar diluents such as ILs. However, in order
M3  3HRext  MR3,ext  3H (3)
to confirm the extraction stoichiometry in ILs, a loading
Some alkyl monocarboxylic acids such as Versatic 10 test was conducted for Y3. Equal volumes of the IL
exist as dimers in organic solvents; the rare earth metals phase containing 6 mol/m3 DODGAA and aqueous
are extracted with such dimers (HR)2 as follows phases with varying Y3 concentrations were equili-
(Dupreez and Preston, 1992): brated. The results, shown in Figure 6, demonstrated

310 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

 Table 1 Equilibrium constants for rare earth metals with DODGAA in ionic liquids and n-dodecane systems (298 K)

Solvents [C4mim][Tf2N] [C8mim][Tf2N] [C12mim][Tf2N] n-dodecane, 5 vol% octanol

Y 9.48  102 2.79 2.86  101 1.12  101

Kex
Eu 4.06  102 1.78 2.45  101 8.15

Fig. 8 Extracting phase recycling. Initial extraction phase:

[DODGAA]IL,0  15 mol/m3, [C4mim][Tf2N]; Aqueous
feed phase: [M]i, 0  0.1 mol/m3; Stripping phase:
1 mol/dm3 HNO3, Y3 (Black), Eu3 (gray)
Fig. 7 Plots of log D versus log ([DODGAA] / [H]). Metal
ions: Y3 (filled symbols), Eu3 (open symbols);
phase was examined. After the extraction of rare earth
solvents: [C4mim] (circle), [C8mim] (diamond),
[C12mim] (square), n-dodecane (triangle); [M]i  metal ions of 0.1 mol/m3 each into [C4mim][Tf2N] with
0.1 mol/m3 15 mol/m3 DODGAA, the metal ions were quantitatively
stripped from the extracting phase into 1 mol/dm3 nitric
acid solution. The IL phase that was separated from the
that the molar ratio of the initial DODGAA concentra- stripping aqueous phase was reused as the extracting
tion to the loaded Y3 concentration approached a con- phase for the next fresh feed aqueous solution. The ex-
stant value of 3 with increasing Y3 concentration in the traction and stripping processes were repeated three
aqueous phase. This result supports the idea that Y3 and times. As shown in Figure 8, no decline in the extraction
Eu3 were extracted to the organic phase as 1 : 3 com- efficiency of the extracting phase was observed, and
plexes with monomer DODGAA as described in Eq. (3). quantitative recovery was achieved after the third stage.
The equilibrium constant of Eq. (3), Kex, is defined These results demonstrate that ILs can be reused as the
as follows: extracting phase in aqueous/IL extraction.
Kex  [M]ext[H]3 / [M]aq[HR]3 (5)
Conclusion
Rewriting Eq. (5) using the definition of D gives:
For the application of ILs to the extraction separa-
log D  log Kex  3log [HR]  3pH
tion of rare earth metal ions, alkyl monocarboxylic acid
 log Kex  3log ([HR] / [H]) (6)
DODGAA was employed as an extractant. DODGAA
As shown in Figure 7, the plots of log D versus was readily dissolved in imidazolium-based ILs, and
log ([HR] / [H]) give straight lines with slope 3 for Y3 quantitative transfer of Y3 and Eu3 to [Cnmim][Tf2N]
and Eu3 in the organic and IL systems. The values of (n  4, 8, 12) was achieved. High extraction perform-
Kex determined from the data in Figure 7 are listed in ance was observed for the metal ions when ILs having
Table 1. The extraction performance of DODGAA for shorter alkyl chains in the imidazolium cation were used,
rare earth metals was enhanced by a factor of 80 in the and the extraction performance in [C4mim][Tf2N] was
[C4mim][Tf2N] system relative to the n-dodecane sys- far superior to that in the conventional organic solvent,
tem. n-dodecane. The metal extraction was found to proceed
2.3 Recyclability of ionic liquid and the recovery of via a proton exchange mechanism in both the ILs and in
rare earth metals the organic solvent. Metal stripping from the IL phase
The reuse of the ILs for recycling the extracting was easily accomplished with an acid solution such as

VOL. 44 NO. 5 2011 311

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