Extraction of rare earth and heavy metals, using ionic

solvents as extraction medium (A Review)

Didier Villemin, Mohamed Amine Didi

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Didier Villemin, Mohamed Amine Didi. Extraction of rare earth and heavy metals, using ionic solvents
as extraction medium (A Review). Oriental Journal of Chemistry, Oriental Scientific Publishing
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 ISSN: 0970-020 X
ORIENTAL JOURNAL OF CHEMISTRY CODEN: OJCHEG
An International Open Free Access, Peer Reviewed Research Journal
2013, Vol. 29, No. (4):
Pg. 1267-1284
www.orientjchem.org

Extraction of Rare Earth and Heavy Metals, Using Ionic

Solvents as Extraction Medium (A Review)
DIDIER VILLEMIN1 and MOHAMED AMINE DIDI2*

1
Laboratoire de Chimie Moléculaire et Thioorganique, UMR CNRS 6507,
INC3M, FR 3038, Labex EMC3, ENSICAEN, 14050 Caen, France.
2
Laboratory of Separation and Purification Technology, Tlemcen University,
Faculty of Sciences, Department of Chemistry,Box 119, Algeria.

http://dx.doi.org/10.13005/ojc/290402

(Received: September 04, 2013; Accepted: October 25, 2013)

ABSTRACT

A review. In this paper, separation of metals with solvent extraction, ionic liquid extraction
phase and chelate extraction of metal ion were reviewed.

Key words: Ionic liquid; Solvent extraction; Metals; chelate, Rare earth metals.

INTRODUCTION need to find a way to recycle it (to extract it) because

China is almost the only supplier with more than
Ionic liquids show unique properties such 95% of the worldwide production of rare earth
as nonvolatility (negligible vapor pressure), thermal metals and they have decided to limit the exportation
stability, nonflammable nature, lower reactivity, forcing people to increase the price of raw
strong ability to dissolve a large variety of organic materials.[1]
and inorganic compounds... That’s why we should
study the potential of it to the extraction of rare earth In this report, we will study the different
(lanthanides plus Sc and Y) and heavy metals. extractions techniques of rare earth metals and after
Indeed, heavy metals are a big problem for industrial the ones for heavy metals.
companies who want to recycle the waste like
mercury or cadmium to be more economically Extraction of rare earth metals
profitable as well as for the environment. There is a Different techniques are used to extract
much bigger application. In fact, the extraction of rare earth metals (REM) and the number of
rare earth metals is becoming more and more publications regarding this topic is increasing. In
important due to the fact that it’s everywhere in this part, we will focus on the extraction using
technological devices like cellphones, television, extractants and another part using coordinated
computers, tablet, permanent magnets... So, we anions in the ionic liquid.
1268 VILLEMIN & DIDI, Orient. J. Chem., Vol. 29(4), 1267-1284 (2013)

RTILs with imidazolium salts combined with different

Room-temperature ionic liquids RTILs are anions like PF6- or NTf2-. They are noted [CnMIM]
the first ionic liquids used to extract metals from with n equal to the number of carbon for the alkyl
aqueous solutions. They’ve become the base for chain on the imidazole (Figure 1).
most of the new ILs made after. Those ILs are made

Fig. 1: [CnMIM][PF6] and [CnMIM][NTf2]

This was the first potential ILs to be used Extraction with extractants
for extraction but their problem is that the solubility First method
of the lanthanides in it is really poor. A lot of examples Charged metal ions are usually insoluble
are present in literature; one of them is the study in hydrophobic ionic liquids (IL), so extractants are
made by Zuo et al in which they studied the potential necessary in the IL’s phase just as in organic solvent.
of those RTIL to separate Cerium from aqueous First workswere about the use of CMPO:
solution containing thorium and lanthanides.[2] Octyl(phenyl)-N,N-diisobutyl carbamoylmethyl
phosphine oxide(Figure 2).[3]
The results showed quite good results for
Cerium but when other lanthanides were tried, the As CMPO is a neutral extractants, an anion
results weren’t good enough. This study proves the (such as NO3-) is required in acidic conditions to
need of the IL to have an extractant to facilitate the extract the cationic metal ions. The IL used was
extraction. [BMIM][PF6] (Figure 3).

Fig. 2: CMPO Fig. 3: [BMIM][PF6]

Three rare earth metals are studied Ce3+, extractability of CMPO is highly better in IL than in a
Eu3+ and Y3+with an increasing concentration of classic organic solvent (the volume of needed
CMPO (black symbols) in comparison to the same extractant is divided by 17).
extraction but in dodecane. They prove that the
 VILLEMIN & DIDI, Orient. J. Chem., Vol. 29(4), 1267-1284 (2013) 1269

The main problem with this kind of process was The AHA, DTPA, EDTA and citric acid have
that after the metals comes to the IL phase, the been chosen because it’s known that they form
extraction of it was hard due to the mechanism in water-soluble complex with many metal ions. The
the IL system. Indeed, the extraction involves cation optimum solution is the number 5. This was the first
exchange between the IL and aqueous phase, and accomplished stripping of lanthanides in literature.
the IL anions in the extracting phase which act as
the counter anions of the extracted phase.

Table 1: The different extractants used

Name Structure Name Structure

Htta: 2-thenoyl TODGA: N,N,N’,N’-

trifluoroacetone tetra(n-octyl)diglycolamide

D2EHPA: Di-(2-ethylhexyl) pH2Et2: diphenyl(diethylcarba

phosphoric acid moylmethyl)phosphine oxide

HDEHDGA: bis(2-ethylhexyl) Bu2Et2: dibutyl(diethylcarbamoyl

phosphoric acid methyl)phosphine oxide

Cyanex 272 HYD: 1-Hydroxy-2,5-

pyrrolidinedione

TPEN: N,N,N’,N’tetrakis Cyphos IL 104R1 = hexyl

R2 = tetradecyl
(2-pyridylmethyl)-ethylenediamine R3 =2,4,4trimethylpentyl

Cyanex 925 PAN: 1-(2-pyridylazo)-

2-naphthol

TPMDPO: tetraphenylmethyle DODGAA:N,N-

dioctyldiglycolamic acid
nediphosphine dioxide

PC-88A
1270 VILLEMIN & DIDI, Orient. J. Chem., Vol. 29(4), 1267-1284 (2013)

Improvements The effects of parameters such as aqueous

Recently, others extractants were studied to organic phase’s volume ratio, metal concentration
to extract specific lanthanides to improve this IL concentration, pH levels, ionic strength, and
difficulty.[4] Some reviews already explained the role temperature were reported10.
and the consequences of the addition of the
extractants.[5]The different extractants are listed in
the Table 1:

The use of Htta was studied by Jensen et

al in 2003.[6] With that goal, they studied trivalent
N H
lanthanides Ln3+ with Htta in RTILs [C4MIM][NTf2]. O
+
- H N
The big advantage of this extractant is the facility to O P O

strip the metal ion from the IL after the extraction. O

This was the first time the recovering of the metal

ions was efficient in the literature.

D2EHPA
The first reproducible study was made by
Yoon et al in 2010 as an extractant in RTILs
[C4MIM][PF6].[7] Five different lanthanides elements Figure 4: Structure of 2-butyl-imidazolium
were studied in their chloride form: CeCl3, NdCl3, bis(2-ethylhexyl) phosphate
SmCl 3, DyCl 3 and YbCl 3.It was proved that the
extractability of lanthanides increases as the ionic
radius of the lanthanides decreases. PC-88A
Continuously with the previous extractants,
Moreover, a quite little quantity of D2EHPA PC-88A (commercially available) was study as
is needed to have a good extraction making this another organophosphorus extractant in RTILs
process not expensive. [CnMIMI] [Tf2N] (n=2, 4, 8, 12).[11] It appeared that
higher extraction efficiency was given by [C8MIM].
D2EHPA– HDEHDGA
A comparison of those two extractants has However, the stripping was easier with
been made by Rout et al in 2011 particularly on [C12MIM] thanks to HNO3.
Americium and Europium8-9. This study showed
extraordinary power of extraction for these metals The extractability of the metal is controlled
in RTIL like [OMIM2][NTf2]. by pH of the aqueous phase. Indeed, in function of
the metal, the pH is not the same. This property was
This study revealed that there is an optimum evaluated by the pH0.5 corresponding to the pH
pH but also that HDEHDGA is superior in terms of needed to extract 50% of the metal.
extractability of metals than D2EHPA. D2EHPA was
before studied with other organophosphorus The problem with that extractant is the poor
extractants but with those results, the tendency solubility of it in the IL.
would be to use derivatives of HDEHDGA.
TPEN
D2EHPA –C4mim TPEN4 is a neutral hexadentate ligand
A novel room temperature ionic liquid (2- effectively coordinating with lanthanides. It’s soluble
butyl-imidazolium di-(2-ethylhexyl) phosphate) in ILs due to the high affinity of the pyridyl groups for
([C4mim][ D2EHPA], figure 4) was synthesized and the ILs and showed high extraction efficiency for
tested as extractant in the mercury (II) liquid-liquid lanthanides.
extraction.
 VILLEMIN & DIDI, Orient. J. Chem., Vol. 29(4), 1267-1284 (2013) 1271

Cyanex 925 This phenomenon can be explained by

This extractant was used by Sun et al with the tridentate diglycolamic acid trapping the metal
the goal to separate Scandium from Yttrium and with big radius. Moreover, high extraction
other lanthanides12. This extractant was first mixed performance was observed for the metal ions when
with A3363 as cation and NO3 as the anion. The ILs having shorter alkyl chains in the imidazolium
only result of this study is the potential of Cyanex cation.
925 to separate Scandium from Yttrium whereas
for the other lanthanides, this extractant is not Finally strippingwas easily accomplished
sufficient enough. with an acid solution in poor proportions such as
nitric acid and the IL is after then reusable.
Cyphos IL 104
This extractant was used in RTIL Another study has the same results as this
[C8MIM][PF6]13. The final IL was synthesized by a one.[17] Indeed, they evaluate the extractability of
sol/gel method. The name of this new IL is B104SG. the whole series of lanthanides and showed the
This extractant showed incredible results compared pH0.5 too for different sizes of alkyl chain.
to the previous one Cyanex 925 (noted IL923SG).
With those results, this extractant needs to be more All the rare earth elements could be
studied in the future. extracted at low pH, but like the previous analysis,
the optimum conditions needs to be defined before
HYD the use of such a system.
This was first studied by Mallah et al and
more recently by Jamali and al.14-15. The difference Finally, the stripping of those elements was
between the two publications is the presence of successfully demonstrated by Baba et al showing
PAN in the mixture to ameliorate the extractability once again that for transition metals, this extractant
of lanthanides with HYD. But this extractant didn’t isn’t good whereas for lanthanides, the extraction
prove real property to extract lanthanides but just and the recovery is quite good.[18]
to create IL which can be used after in a DLLME:
Dispersive liquid-liquid micro-extraction. This extractant is a promising one to the
recovery of rare earth metals in waste solutions.
DODGAA and TODGA Recently, this extractant has been used to form
Those extractants are members of the membranes to ameliorate the extraction processes.
same family and have similar properties. TODGAA
was the first to be studied4it has high affinity for The others
lanthanides in RTIL systems. Its extraction ability Some of others extractants mentioned
was strongly demonstrated although the selectivity earlier have been studied such as Cyanex 272,
in the lanthanide series was different. TPMDPO added with Ph2Et2 or Bu2Et2. But they’re
still not sufficient enough to be interesting in the
However, the stripping and the recovery recycling of rare earth metals from waste.[19]
of the TODGA were not sufficient enough. That’s
why its analog, DODGAA, was studied16. It has a Extractions using ionic liquids with coordinated
molecular structure in which one of the two anions
carbamoyl groups in TODGA is replaced by a The main problem of ionic liquids with
carboxyl group. It is soluble in RTIL and has high weakly coordinated anions is that the metal salts
affinity for rare earth metals. They try different RTIL are poorly soluble in them. A solution to this problem
to evaluate the potential of DODGAA ([CnMIM], n=4, is to attach functional groups to the cationic core.
8, 12). That’s what Nockemann et al studied in a recent
publication20. They showed that hydrophobic ionic
This study shows two important things: liquids can be obtained by using the
´ The high extractability for lanthanides hexafluoroacetylacetonate anion [hfac]. In this study,
´ The poor one for Zn. cations are imidazolium salts and several member
1272 VILLEMIN & DIDI, Orient. J. Chem., Vol. 29(4), 1267-1284 (2013)

of this family have been studied: [C x min] most hydrophobic compound). This extraction
(x=2,4,6,8,10,16,18) represented in the Figure 5. process occurred at the interface between the two
liquid phases without stirring.

Instantaneously after the addition of

neodymium, the ionic liquid changes color
explaining by the fact that there is a transfer of Nd3+
between the two phases. The final step of this
extraction is the formation of a complex [Nd(hfac)4]
in the ionic liquid phase. A crystal structure of this
complexe was made showing that the neodymium
is surrounded by four bidentately coordinating
Fig. 5: [Cnmim][hfac] diketone anions in a quadratic antiprismatic
geometry.
Those ionic liquids were prepared y a
methathesis between an organic chloride salt and The acidic hydrogen atom forms hydrogen
ammonium hexafluoroacetylacetonate in bond with the oxygen making this complex even
acetonitrile. The precipitate was filtered and the more stable. That’s why this process is so efficient.
acetonitrille solvent was removed under reduced
pressure. The residue was then redissolved in Another study was made by Binnemans et
dichloromethane and washed with water and re- al showing an improvement into solubilizing
evaporated to obtain the pure ionic liquid. It is lanthanides into ionic liquids which is the main
noticeable that the ionic liquid is better when the problem with lanthanides and ionic liquids.[23] With
alkyl chain is a butyl or even longer to reinforce the that intention, the synthesis of [Ln(NCS)4(H2O)y]3-x
hydrophobicity. (x=6-8, y=0-2) was made by a metathesis procedure
starting from stoichiometric amounts of
This study, based on neodymium, cobalt lanthanides(III) perchlorate, ammonium
and copper, showed excellent results to extract thiocyanate, and thiocyanate ionic liquid with the
metals. An aqueous solution of neodymium salt was corresponding imidazolium salt. The thiocyanate
poured on top of a sample of the ionic liquid was introduced to ameliorate the solubilization of
[C4min][hfac] (with a butyl chain because it was the the lanthanide into the ionic liquid.

Fig. 6: Structure of [BMIM]x-3[Ln(NCS)x(H2O)y]3-x(x=6-8; y=0-2, BMIM=1-butyl-3-methylimidazolium

This study showed great results and almost functionalized imidazolium. That’s what Vicente et
all lanthanides was extracted by this process by the al studied in 2012.[21]
creation of a new ionic liquid. The main problem of
this process is that the ionic liquid is not regenerate According to Scheme 1, they synthesized
at the end of the process. those ILs in two steps, using alkyl bromide-
functionalized 1,2 dimethyl-imidazolium ionic liquid
The second view of extracting rare earth with [Tf2]- and potassium diphosphine. The resulting
metals with extractants are the phosphine oxide phosphine is oxidized by hydrogen peroxide to give
the desired [DMImCnP(O)Ph2][NTf2].
 VILLEMIN & DIDI, Orient. J. Chem., Vol. 29(4), 1267-1284 (2013) 1273

Scheme 1

When this new IL is in contact with a This property shows the potential of these new ILs
solution of Eu(hfac)3.6H2O, there is the formation in the extraction process of lanthanides, actinides
of crystal which is the complex of Eu(hfac) 4 or transition metals.
(DMImCnP(O)Ph2). The structure of this complex is Finally, Nockemann et al are studying the
shown on Figure 7. It surprisingly indicates that extraction of lanthanides using trihexyltetradecyl
those new ILs have the ability to be tuneable for phosphonium [P666 (14)]+ (Figure 11) as cation to trap
lanthanides. lanthanides by making new ionic liquids containing
lanthanides, allowing it to extract the metal from
water.[22]

Fig. 7: structure of the Europium complex Fig. 8: [P666 (14)]+

Fig. 9: Structure of the new IL composed with [P666(14)]+

1274 VILLEMIN & DIDI, Orient. J. Chem., Vol. 29(4), 1267-1284 (2013)

They studied a lot of lanthanides. But the

major application of this is not the extraction of
lanthanides but the realization of OLED materials
for futures screens.

The structure of the final IL created is in

the Figure 9. As we can see, this is the evolution of
the previous Europium complex.

Task specifics ionic liquids

Task –Specific Ionic Liquids (TSIL) are ionic
liquids with functional group covalently tethered to Fig. 10: Betaine
the cationic or anionic part. When the functional
group has the ability to coordinate to the metal ion
(preferably as a bidentate or a polydentate liguand),
it is easier to dissolve metal oxides or metal salts
into the ionic liquids. The major drawback of these
TSIL is that they are often only accessible after
multistep synthetic procedure. In a search for cheap
and easily accessible cationic building blocks for
ionic liquid alternatives, Binnemans et al tried to
make TSIL with betaine.[23] Betaine is the trivial name
for 1-carboxy- N,N,N -trimethylmethanaminium. Fig. 11: [Hbet][Tf2N]
(Figure 10).
Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb4O7, Dy2O8, Ho2O3,
ith that intention, they introduced Er2O3, Tm2O3, Yb2O3, Lu2O3, UO3, PbO, ZnO, CdO,
protonated betaine with bis(trifluoromethysulfonyl) HgO, CuO, Ag2O, NiO, PdO and MnO.[22] The metal
imide, [Hbet][Tf2N], as a potential new TSIL for oxide is mixed with [Hbet][Tf2N] and water and it’s
selective solubilization of metal oxides and metal stirred at room temperature for several hours. It
salts (Figure 11). appeared that not all metal oxides were soubilized
in [Hbet][Tf2N]. Insoluble or very poorly soluble are
The solubility of different metal oxides and iron, manganese and cobalt oxides as well as
metal salts has been studied. It appeared that this aluminum and silicon oxides. This property can be
kind of TSIL is sensible of temperature and pH. explain by the fact that the metal oxide reacts with
Indeed, [Hbet][Tf2N] forms a two phases system with the carboxylic acid group of the ionic liquid to form
water at room temperature and slightly above but a carboxylate complex into water.
when it’s hotter, it’s a one-phase mixture.
Then, the metal can be stripped from
This is the same problem with the pH. betaine by extracting the ionic liquid by an acidic
Indeed, when the pH is around 8, the TSIL and the aqueous solution of diluted hydrochloride or diluted
water form a one-phase mixture whereas it’s a two- nitric acid. The metal complex of protonated betaine
phase mixtures when the pH is equal to 1.5. This is decomposed and the betaine ionic liquid is
property shows the obligation to work in an acidic regenerated. The ratio of the metal content in the
solution to extract metal oxides. aqueous phase to the ionic liquid phase is 1:82
after the first extraction. After a second one, almost
When those properties are established, it’s all the metal is extracted.
interesting to study the ability of [Hbet][Tf2N] to
dissolve metal oxide. So, Binnemans et al , [Hbet][Tf2N] can be formed towards several
demonstrated that this system is able to dissolve synthetic routes. The main one is by reaction of the
the following oxides: Sc2O3, Y2O3, La2O3, Pr6O11, zwitterionic betaine with the acid hydrogen and
 VILLEMIN & DIDI, Orient. J. Chem., Vol. 29(4), 1267-1284 (2013) 1275

Tf 2NH. This reaction involves a simple proton earth metals. The major products are made with
transfer from the bis(trifluoromethylsulfonyl)imide BMIM or CMIM. The question was the influence of
to the more basic carboxylate group, so that the the alkyl chain on the extraction process. With that
betaine will be protonated. This is a general method, intention, Germani et al studied the effects of the
applicable for the preparation of other betaine salts. alkyl chain on ILs composed of CnMIM (Figure 12)
for the extraction of mercury.[24]
Extraction of heavy metals
Heavy metals are big challenges in
industry because of the wastes produced by the
fabrication of various products. Those wastes are a
problem for environment: we need to extract them
to reuse it. In this part, we will study different ways
to accomplish that.

RTILs
The room-temperature ionic liquids,
RTILs, are formed by imidazolium salts with alkyl
chain. This is the same process that for the rare

Table 2: Ion percentage of Hg2+ Fig. 12: [CnMIM] , n=4,6,8

at 60°C as a function of time
Mercury was chosen because of its facility to be
extracted by that kind of IL. This study showed that
Time % Hg (II) in IL
longer the chain is, better the extraction is (Table
(h) [C4MIM] [PF6] [C6MIM] [PF6] [C8MIM] [PF6] 2).

4 70 62 90 The second parameter studied was the

6 79 76 94 temperature. Indeed, they showed that lower the
8 86 82 97 temperature is, higher the time of extraction is
12 97 97 100 (Figure 13).
24 98 100 -
30 100 - -

Fig. 13: Extractability of Hg as function of the temperature

1276 VILLEMIN & DIDI, Orient. J. Chem., Vol. 29(4), 1267-1284 (2013)

So, to have better conditions for that kind of A crystal structure was also made,
extraction, we need to have long alkyl chain like showing that the cobalt(II) ion is octahedrally
octyl and temperature around 60°C. surrounded by three hexafluoroacetylacetonate
anions.
Coordinated anions:
This is the same process as earlier, with Addition of extractant
rare earth metals.[24] After the reaction at the interface 2-aminothiophenol
between [C4min][hfac] and a solution of Cobalt, two An improvement of the previous works has
phases are observed and a change of color for the been made by Lerlapwasin et al added the 2-
ionic liquid instantaneously after the addition of the aminothiophenol as an extractant into a RTIL 1-
cobalt complex. butyl-3-methylimidazolium hexafluorophosphate
[BMIM][PF6]( Figure 14:2-aminothiophenol;Figure
15:[BMIM] [PF6]. [25]

Fig. 14: 2-aminothiophenol Fig. 15: [BMIM][PF6]

This addition of extractant improves the of metals in RTIL composed with imidazolium
extraction percentage of Ni, Cu and Pb (Table 3: salts.[26-27]
Values of Extraction).

The percentage of Pb is still low but this is

the best actually. After the extraction I the ionic liquid,
we need to strip the metal from the IL. It was proved
that with the addition of nitric acid, the stripping level
is high.

Table 3: Values of Extraction Fig. 16: Dithiozone

This study is surprising in the sense that
Metal ion %E
all others publications showed that the acidic pH is
important but in this one, a basic pH is better to
Ni2+ 57
extract.
Pb2+ 20
Cu2+ 76
This process is proved to be reproducible
Dithiozone and efficient towards some metals. Besides, the IL
Dithiozone (Figure 16) are sulphur can be used again by stripping the metal from the IL
compounds used by Chen et al to improve extraction by nitric acid.
 VILLEMIN & DIDI, Orient. J. Chem., Vol. 29(4), 1267-1284 (2013) 1277

Aza-Crown ether
This extractants have been studied by
Huimin et al.[28] The structures are based on crown
ether but with a nitrogen atom in the ring. The best
results were obtained with N-Dodecyl Aza-18-
crown-6 (Figure 17).

In way to study the extractability of some

metals (Sr2+, K+, Cs+, Na+), the aza crown-ether was
added in four different RTIL based on imidazolium
salts [CnMIM][NTf2] (n=2,4,6,8). This study revealed
Fig. 17: N-Dodecyl Aza-18-crown-6
the high power of aza crown-ether to extract
particularly strontium. These observations demonstrate that the
extraction system based on N-alkyl aza-18-crown-
Those results prove that the best extraction 6 (especially dodecyl) in ILs offer not only easier
process is the addition of the aza crown-ether with recycling strategy but also better selectivity toward
an imidazolium salt composed with an alkyl chain Sr2+.
of two or four atoms.
Task specific ionic liquid
The problem with that process is the price First try
of the extractant. That’s why they also studied the TSIL for the elective liquid/liquid extraction
recycling of it. With a simple stripping of the metal of heavy metals from aqueous systems were first
with the addition of an aqueous phase containing published by Rogers et al in 2001.[29] Functionalized
nitric acid, the recovery of the metal is excellent imidazolium cations with thioether-, urea- or
which allows this process to be reproducible and thiourea-derivatized side chains act as metal
profitable. ligating moieties, whereas PF6- anions provides the
desired water immiscibility. (Figure 18)

Fig. 18: Thiourea-derivatives ionic liquid

Mercury(II) and Cadmium(II) were targeted as the bulk or may be doped as an extractant into
with the goal to find alternative separations less expensive IL such as [C4mim][PF6]. The best
strategies for removing these toxic metal ions from ILs used are listed in the following figure:
the environment.[30] Those IL can be used directly

Fig. 19: structures of the cations combined after with PF6

1278 VILLEMIN & DIDI, Orient. J. Chem., Vol. 29(4), 1267-1284 (2013)

In each case, they try to extract Hg2+ and This table shows that 1 is a good
2+
Cd directly using the IL and secondly by using extractants for both mercury and cadmium and with
[C4mim][PF6] with a 1:1 ratio and a pH at 1 or 7. or without [C4mim][PF6]. However, with the derivative

Table 4: Extraction efficiency for different composition of IL

IL M2- pH (aq) Distribution ratio System

1 Hg2+ 1 200 1 only

Cd2+ 1 300 1 only
1 Hg2+ 1 170 1+ [Crmim] [PF6] (1:1)
Cd2+ 1 310 1+ [Crmim] [PF6] (1:1)
1 Hg2+ 1 210 1 only
Cd2+ 1 380 1 only
1 Hg2+ 1 210 1+ [Crmim] [PF6] (1:1)
Cd2+ 1 360 1+ [Crmim] [PF6] (1:1)
2 Hg2+ 1 350 2 only
Cd2+ 1 20 2 only
2 Hg2+ 1 74 2+ [Crmim] [PF6] (1:1)
Cd2+ 1 0.0086 2+ [Crmim] [PF6] (1:1)
2 Hg2+ 1 340 2 only
Cd2+ 1 23 2 only
2 Hg2+ 1 100 2+ [Crmim] [PF6] (1:1)
Cd2+ 1 0.0074 2+ [Crmim] [PF6] (1:1)

2, the ratios are lower than with 1 and it’s much less about the superiority of 1 and 2 can be explained
effective at extraction of Cd2+. Besides, 2 doesn’t by the interaction between the S atom in the alkyl
extract Cd2+ when it’s diluted with [C4mim][PF6]. So, chain, able to react with the metal. With those results,
2 is more selective than 1 what’s could be a big others derivatives have been made: Figure 20.
advantage in an extraction process. The results

Figure 20: structure of imidazolium derivatives

 VILLEMIN & DIDI, Orient. J. Chem., Vol. 29(4), 1267-1284 (2013) 1279

All those IL have the same behavior as extractants producing toxic and corrosive HF or fluorides.
for mercury and cadmium when they’re mixed in Moreover, those ionic liquids are expensive due to
equal ratio with [C4mim][PF6]. In general, the ratios the price of starting materials. Besides, we still need
of Cd are lower than observed with Hg. to find a way to strip the metal from the IL phase.

It is noticeable that both alkyl chains TOAH

appear to affect the extraction 4 and that the TOAH, trioctylammonium are a new kind
adjustment of pH in acidic conditions doesn’t of ILs. TOAH (Figure 21) has they are composed of
facilitate stripping of cadmium but practically doesn’t four alkyl chains on the ammonium with three octyl
affect mercury. groups and one hydrogen.

It appears that increasing the alkyl chain

length from butyl to octyl increases the
hydrophobicity of the IL which ameliorates the ratio.
Besides, the hydrophobic environment may prevent
the hydrolysis.

To complete this study, tests have been

made with different concentration of IL in
[C4mim][PF6].

That kind of IL shows excellent results for

extraction, but the problem is the instability of the
Fig. 21: TOAH
hexafluorophosphate anion by hydrolysis

Table 5: Extraction percentage of metals with

a mixture of [TOAH][NO3] in [TOAH][NTf2] at 25°C

Concentraiton of Rh(III) Pd (II) Cd(II) Pt(IV)

Hcl (mol dm-3) E (%) E (%) E (%) E (%)

0.10 4.6 99.8 0.5 92.5

1.0 4.0 96.7 54.2 92.7
2.0 4.6 92.6 67.7 86.7
4.0 1.3 81.9 68.5 79.0

A study from Katsuka et al shows excellent This table shows that for each metal, the
results for Platinum and Palladium. But the results dependency of pH is not the same. In fact, for Pd,
were even better when there was two different ionic the concentration of HCL needs to be not too high
liquids of TOAH were mixed. The difference between whereas for the Cd it’s the contrary. A compromise
the two ILs, was the anion.[31] for each metal needs to be made to find the perfect
process.
Another factor needs to be
considered: the pH. Indeed, as the TOAH is an Concerning the back extraction of the metal
ammonium, the acidic proton on the ammonium from the IL, a simple stripping with nitric acid is
can be removed if the pH isn’t acid enough. With enough for most of the metals. But some of them,
that optic, Katsuka and co-workers have studied like the palladium, the recycling is not so efficient
the power of pH on the extractability for several or we need to provide really high concentration of
transition metals. The following table is giving results n nitric acid.
for some of them.
1280 VILLEMIN & DIDI, Orient. J. Chem., Vol. 29(4), 1267-1284 (2013)

So, TOAH has high extractability in acidic known as TOMATS are the better results today for
condition than general hydrophobic ionic liquids the extraction of heavy metals adapted from the
and the major advantage is the control of the TOAH derivatives. The difference is the longer alkyl
extractability by the composition of the mixture. chain on the fourth substituent.
Besides, Most of the metals extracted in the IL can
be stripped through back-extraction with aqueous This is the novel high-performance, TSIL
nitric acid solution to regenerate IL. for the extraction of heavy metals from aqueous
solution. To overcome the previous problems,
TOMATS TOMATS (Figure 22) contain no fluorine and is
Trioctylmethylammonium thiosalicylate absolutely stable towards hydrolysis.

Fig. 22: TOMATS

Table 6: The TOMATS and derivatives

Name/Symbol Structure Name/Symbol Structure

Tricaprylmethyl Tricaprylmethyl

ammoniumthiosalicylate ammonium
[A336][TS] 2-(methylthio) benzoate
[A336][MTBA]

Tricaprylmethylammonium

benzoate Tricaprylmethylamm
[A336][BA] onium
Hexanoate
[A336][Hex]

Tricaprylmethylammonium Trihexyl(tetradecyl)

Thiocyanate phosphonium 2-
[A336][SCN] (mercapto)Benzoate
[PR4][MTBA]

Trihexyl(tetradecyl) Trihexyl(tetradecyl)

Phosphonium salicylate phosphonium 2-

[PR4][Sal] (methylthio)Benzoate[PR4][MTBA]
 VILLEMIN & DIDI, Orient. J. Chem., Vol. 29(4), 1267-1284 (2013) 1281

The efficiency of TOMATS can be between the contact time of IL and metals and the
explained by the chelating effect of the ortho- extraction efficiency.
substituted carboxylate group relative to the thiol
functionality.The bigger advantage is the facility to Another factor influences the extraction
produce it at industrial scale. The first application is efficiency is the pH. As it was demonstrated earlier,
the extraction of copper from an aqueous Cu2+- an acidic pH doesn’t facilitate the extraction.
tetramine phase. After the addition of TOMATS, two
phases are seen: one with copper-free region and According to those results, TSIL TOMATS-
a dark copper-containing upper region. After shaking derivatives represent a good procedure for
and separation of the phases, all the copper is selective cleaning of contaminated waste water. In
extracted into the upper phase (third test tube).[32] particular, thiol, thioether- functionalized are efficient
for instance for communal waste cater. But, for
It is noticeable that sometimes separation industrial water, full of Zn, it’s recommended to use
takes quite a long time due to the high viscosity of [A336][SCN]. Although those ILs are efficient, the
TOMATS. This can be avoiding by the addition of problem still is the price of the extraction due to the
immiscible organic solvent or by gentle heating of price of the ILs.
the mixture. Moreover, it can be improved by using
centrifuge or adding small amount of sodium sulfate That study is the following of a previous
to the aqueous phase before shaking. one made by Kalb et al in 2006, where they could
extract heavy metals (principally mercury) from
Most recently studies made by Hann and waste water using the commercially available
co-workers , used TOMATS as extraction ionic TOMATS.[34] They also proved that TOMATS can
liquids from industrial water. The evaluation of the extract heavy metals by forming metal-thiolate and
potential of anion functionalized IL as extracting additionally a complex-bond with the carboxylate
agents for Cd, Ni, Hg, Pb… was studied.[31] With group of the thiosalicylate anion, favoring the
that intention, different TOMATS have been made, extraction process.
listed in the Table 6.
The high extractability of Ag Hg has been
After 120 minutes of extraction, the ILs already demonstrated by Papaiconomou et al in
revealed high extraction efficiency for Ag, Hg and 2008 with pyridines and piperidines derivatives
Pt, whereas only a limited fraction of As, Cr and Ni ILs.[35] With that intention, they synthesized several
could be eliminated from the solutions. new types of Ils summarized in the Figure 23.

The high extractability of mercury is due

to the fact that it’s soluble either in functionalized or
unfunctionalized ILs. The similar tendency is
observed for Ag. Interestingly, Cd, Pb and Zn could
be partially eliminated from the model solution by
[PR 4 ][TS] but there was no effect on the
corresponding ammonium cation with the same
anion [A336][TS]. So, it appeared that both cation
ring and anion are strongly influencing the metal
extraction from water. Generally, the extraction Fig. 23:
efficiency was higher for IL with [TS], [MTBA] or
[SCN] than those with [BA], [hex] or [sal] indicating After the study of RTILs 1, they studied the
that the sulphur containing functional groups same property for the ILs 2 to 4.The results are that
strongly affect the extraction efficiency. This property except for mercury, ILs containing pyridinium
was already shown with others ILs.[33] cations have poor extraction activity. However, TSILs
containing a nitrile functionappear to be good and
It is noticeable that there is a correlation selective extracting agents for silver and palladium
1282 VILLEMIN & DIDI, Orient. J. Chem., Vol. 29(4), 1267-1284 (2013)

ions. Finally, piperidines cations don’t show any CONCLUSION

amelioration toward the extraction compared to the
same with pyridinium cations. Nowadays, rare earth elements and heavy
metals are big challenges for industries both
Egorov et al. studied the extraction property environmentally and economically with the
of TOMATS toward Iron(III) and Copper(II).[36] The increasing demand of rare earth elements. This work
findings were that Iron and Copper are the most listed the different techniques used to extract them
stable salicylate complexes so the results of from aqueous solution with the goal to reuse those
extractions were high. However, for Nickel and metals after their extraction in wastes.
Manganese, the ratios were low due to their poor
stability as complexes. Some promising techniques have been
demonstrated like the task-specific ionic liquids for
Finally, binary mixtures of the ionic liquid both heavy metals and rare earth elements.
betainium bis(trifluoromethylsulfonyl) imide and
water show an upper critique solution temperature37. Moreover, processes about the recovery
This solvent system has been used to extract metal of the metal from the IL extractant phases have been
ions by phase-transition extraction, using realized with excellent results. The only problem
zwitterionic betaine as extractant. The system is which remains is the price of the TSILs.
efficient for the extraction of trivalent rare-earth,
indium, and gallium ions. This new type of metal Finally, new applications are coming up
extraction system avoids problems associated with for the use of IL in the recovery of nuclear wastes
the use of viscous ionic liquids. giving encouraging results.[38]

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