Article

Cite This: Ind. Eng. Chem. Res. 2018, 57, 1621−1629 pubs.acs.org/IECR

Task-Specific Ionic Liquids as Extractants for the Solvent Extraction

of Molybdenum(VI) from Aqueous Solution Using Different
Commercial Ionic Liquids as Diluents
Esteban Quijada-Maldonado,*,† Felipe Sánchez,† Bárbara Pérez,† Ricardo Tapia,‡ and Julio Romero†
†
Laboratory of Membrane Separation Processes (LabProSeM), Department of Chemical Engineering, Universidad de Santiago de
Chile, Avda. Libertador Bernardo O’Higgins 3363, Estación Central, Santiago, Chile
‡
Faculty of Chemistry, Pontificia Universidad Católica de Chile, Avda. Libertador Bernardo O’Higgins 340, Santiago, Chile
*
S Supporting Information

ABSTRACT: In this work, the recovery of molybdenum(VI)

(Mo) from aqueous solutions was carried out by solvent
extraction (SX) using ammonium and phosphonium-based
task-specific ionic liquids (TSILs) as extractants diluted in
kerosene and two other hydrophobic room-temperature ionic
liquids (RTILs). Four different TSILs were used as extractants:
trioctylmethylammonium bis(2-ethylhexyl) phosphate
[TOMA][D2EHP]; trioctylmethylammonium benzoate [TOMA][BA]; trihexyltetradecylphosphonium bis(2-ethylhexyl)
phosphate [P6,6,6,14][D2EHP]; and trihexyltetradecylphosphonium benzoate [P6,6,6,14][BA]. These TSILs were synthesized to
assess the effect of the cation and anion on the SX of Mo(VI). Experimental results indicated that high extraction percentages of
Mo(VI) were obtained with all the synthesized TSILs. Besides that, the best cation was [TOMA]+ for all the diluents and [BA]−
was the best anion when kerosene and 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [omim][Tf2N], were the
diluents. Furthermore, the SX process using these ionic liquids followed an anion-exchange mechanism for kerosene and
[omim][Tf2N] as diluents. Finally, the stripping was successfully performed with a solution of ammonium carbonate, and the
extent of stripping depended on the selected diluent.

1. INTRODUCTION
Molybdenum(VI), Mo(VI), is a transition metal that exhibits
many industrial applications such as the forming of nickel-based
super alloys, within the hydrodesulfurization of petroleum,
engine lubrication, and so on. Molybdenum is selectively
recovered from acid leach solutions by means of solvent
extraction (SX) using either alkylphosphonic acids, 1−4
oximes,5−9 or alkylamines.10−12 These extractants are normally
dissolved in kerosene or similar organic solvents which show
several drawbacks such as high volatility, flammability, and
toxicity. Lately, room-temperature ionic liquids (RTILs) have
been proposed as an alternative to those organic solvents in SX
because of their excellent properties, such as negligible vapor
pressure, nonflammability, and in some cases, remarkable
hydrophobicity. RTILs have already been used as diluents in
previous works. For instance, the ionic liquids 1-butyl-3-
methylimidazolium hexafluorophosphate [bmim][PF6] and the
liquid 1-butyl-3-methylimidazolium bis-
(trifluoromethylsulfonyl)imide [bmim][Tf2N] have been ap-
plied as the diluent in the extraction of alkaline metals,13,14
uranyl ions,15−17 rare-earth elements,18,18−23 nickel, copper,
and lead,24−28 iron,29 and gold,30 among others. The
aforementioned ionic liquids provide high hydrophobicity,
relatively low viscosity, and poor coordinating ability;31 the
latter advantage would not allow these ionic liquids to extract
metal ions by themselves. However, in those previous works,
the ionic liquids were used only as diluents in combination with
organic extractants. Recently, the use of task-specific ionic
liquids (TSILs) as extractants has gained attention because of
the high-produced distribution coefficients, as well as potential
selectivity in the SX process. Normally, in these works, the
anion of an ionic liquid is functionalized with a specific group to
extract metal species. For instance, the ionic liquids
tetrabutylammonium bis(2-ethylhexyl)-phosphate, [N4,4,4,4]-
[D2EHP], and tetraoctylammonium bis(2-ethylhexyl)-phos-
phate, [N8,8,8,8][D2EHP], were used as the extractants to
recover lithium;32 trihexyl(tetradecyl)phosphonium benzoate
[P6,6,6,14][BA] was used to extract rare earths;33−35 and
trihexyltetradecylphosphonium 2-(propylthio)benzoate
[P6,6,6,14][PTB] and 2-(benzylthio)benzoate [P6,6,6,14][BTB]
were reported to extract transition metals36 and diketanoate-
anion-based ionic liquids for the extraction of Eu(III) and
Am(III).37 Most of these studies have used neat TSILs without
a diluent, and a few others have used TSILs in combination
with molecular diluents producing high values of extraction
percentage. In these cases, the stripping of the extracted metal
from the ionic liquid phase was difficult because the metal ion
Received: October 5, 2017
Revised: December 28, 2017
Accepted: January 11, 2018
Published: January 11, 2018

© 2018 American Chemical Society 1621 DOI: 10.1021/acs.iecr.7b04147

Ind. Eng. Chem. Res. 2018, 57, 1621−1629
Industrial & Engineering Chemistry Research
solvated by the TSIL showed high stability in the diluent,
limiting the use of these ionic liquids for industrial applications.
More recently, a new kind of extraction of metal ions, using
TSILs diluted in ionic liquids as diluent, has attracted attention
because this extraction system is free of organic solvents.38,39 In
our previous work, it was demonstrated that the right selection
of an ionic liquid as diluent could modify the distribution
coefficient of the SX process facilitating the stripping of the
metal.40 Therefore, the use of TSILs diluted in RTILs would
create a tunable extracting solution.
Therefore, the main objective of this work was to assess the
effect of the cation and the anion of synthesized TSILs used as
the extractants on the SX of Mo(VI) diluted in different
diluents. For this purpose, two ammonium-based and two
phosphonium-based TSILs were synthesized: trioctylmethy-
lammonium bis(2-ethylhexyl) phosphate [TOMA][D2EHP];
trioctylmethylammonium benzoate [TOMA][BA]; trihexylthe-
tradecylphosphonium bis(2-ethylhexyl) phosphate [P6,6,6,14]-
[D2EHP]; and trihexylthetradecylphosphonium benzoate
[P6,6,6,14][BA]. These TSILs were selected because of their
high hydrophobicity and because the anions [D2EHP]− and
[BA]− provide a coordinating ability.31 These ionic liquids were
dissolved in three diluents: kerosene and two RTILs, that is, 1-
butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
[bmim][Tf 2 N] and 1-octyl-3-methylimidazolium bis-
(trifluoromethylsulfonyl)imide [omim][Tf2N]. Additionally,
the solvent extraction mechanism and the stripping of the
Mo(VI) from the loaded phase were determined.
2. EXPERIMENTAL PROCEDURE
2.1. Materials, Apparatus, and Sample Preparation.
For the synthesis of the TSILs, methyltrioctylammonium
chloride (≥97% purity), trihexyltetradecylphosphonium chlor-
ide (≥95% purity), and bis(2-ethylhexyl) phosphoric acid
(≥97% purity) were purchased at Sigma-Aldrich and used
without further purification. Benzoic acid (≥99.7% purity) was
obtained from Winkler Chile. The molybdenum solution was
prepared from sodium molybdate dehydrate with a purity
higher than 99% (Sigma-Aldrich). The diluents used in this
work were 1-butyl-3-methyl-imidazolium bis-
(trifluoromethylsulfonyl)imide (≥99% purity) and 1-octyl-3-
methyl-imidazolium bis(trifluoromethylsulfonyl)imide (≥99%
purity) which were purchased at Iolitec GmbH. Kerosene
(Shellsol) was kindly provided by Minera Michilla Chile.
An analytical balance with a precision of ±0.0001 g (Denver
Instruments Company, model AA200) was used to prepare the
solutions. pH measurements were performed using a pH meter
from Hanna Instruments (Model HI 4212) with a HI 1083B
microelectrode also from Hanna Instruments. The equipment
resolution is ±0.001. The concentration of molybdenum in the
aqueous solutions before and after extraction was quantified by
an atomic absorption spectrophotometer (AAS) (GBC
Scientific Equipment model SensAA dual beam, equipped
with a 4 mA lamp (single element) Photron International). The
equipment resolution is ±0.1 mg/L. The water content in the
ionic liquid before and after the extraction experiments was
quantified using a Karl Fischer Titrator model 831 Coulometer.
Finally, after the synthesis of the TSILs, 1H NMR, 13C NMR,
and 31P NMR spectra were obtained on a Bruker AM-400
spectrometer. The chemical shifts were expressed in ppm
(11.74 T, 400 MHz to 1H and 126 MHz to 13C) downfield
from TMS (tetramethylsilane). A Raleigh Model UV 1800
UV−vis device was used for the quantification of sulfate ions.
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The aqueous solution was prepared by dissolving molybde-
num salt in Milli-Q water (18.2 mΩ) in a volumetric flask. The
pH of this solution was adjusted by adding diluted sulfuric acid.
The organic phase was prepared by mixing the ionic liquids
used as extractants in kerosene or [omim][Tf2N]. The
concentration of the extractant in the diluent was measured
using an analytical balance.
2.2. Synthesis of the Ionic Liquids. The synthesis of the
TSILs was carried out by means of ion-exchange reactions at 20
°C according to previously reported methodologies.41
The ionic liquid [TOMA][D2EHP] was synthesized in two
steps. First, sodium hydroxide and trioctylmethylammonium
chloride were separately dissolved in 2-propanol and then
mixed in a round-bottom flask. This solution was then stirred
for 24 h at 25 °C. The obtained product of this reaction was
[TOMA][OH]. Subsequently, this solution was filtered in a
Celite Filter. Second, a solution of bis(2-ethylhexyl) phosphoric
acid was equilibrated with 2-propanol and then mixed with the
filtered [TOMA][OH] solution in a 1:1 mole ratio. The
mixture was stirred for 24 h in a round-bottom flask. Finally,
the solvent was evaporated in a rotary evaporator at 80 °C and
100 mbar. The obtained product was [TOMA][D2EHP] as a
yellowish viscous liquid.
The synthesis of [TOMA][BA] was conducted in a single
reaction step. First trioctylmethylammonium chloride (1 equiv)
and sodium benzoate (1.03 equiv) were mixed in a Milli-Q
water/2-propanol mixture (50/50 v/v). This mixture was
stirred for 24 h at 30 °C. After this step, the solvent was
evaporated in a rotary evaporator at 80 °C and 60 mbar. Finally,
the obtained ionic liquid was dissolved in chloroform and then
refluxed five times with Milli-Q water. The chloroform was
evaporated in a rotary evaporator at 80 °C and 200 mbar.
On the other hand, the synthesis of [P6,6,6,14][BA] was
conducted by dissolving trihexyltetradecylphosphonioum chlor-
ide (1 equiv) in a mixture of Milli-Q water/2-propanol (70/
30% v/v). Also, sodium benzoate (1.03 equiv) was dissolved in
a mixture of Milli-Q water/2-propanol (50/50% v/v). Once
both salts had been dissolved, they were mixed in a round-
bottom flask and stirred for 24 h at 30 °C. After that, the
solvent was evaporated in a rotary evaporator at 80 °C and 60
mbar. Finally, the resulting ionic liquid was dissolved in
chloroform and washed with five volumes of Milli-Q water. The
chloroform was evaporated at 80 °C and 2400 mbar. The
obtained ionic liquid was a transparent and viscous liquid.
Finally, to prepare [P6,6,6,14][D2EHP], sodium hydroxide and
trihexyltetradecylphosphonioum chloride were separately equi-
librated in 2-propanol. Once dissolved, these solutions were
mixed and stirred for 24 h at 25 °C. After this step, the resulting
solution was filtered using a Celite filter. Along with this, a
solution (1 equiv) of bis(2-ethylhexyl)phosphate acid in 2-
propanol was also prepared. The filtered solution and the latter
one were mixed and stirred for another 24 h at 25 °C. Finally,
the solvent was evaporated in a rotary evaporator at 80 °C and
100 mbar.
[TOMA] [D2EHP]. 1H NMR (400 MHz, CD3COCD3, ppm):
0.90−1.0 (m, 21H, 7CH3), 1.25−1.35 (m, 46H, 23CH2), 1.40−
1.45 (m, 2H, 2CH), 1.50−1.65 (m, 6H, 3CH2), 3.29 (s, 3H,
NCH3), 3.50−3.60 (m, 6H, 3N−CH2), 3.80−3.85 (m, 4H,
2OCH2). 13C NMR (100 MHz, CD3COCD3, ppm): 10.54,
13.51, 13.57, 22.44, 28.83, 28.99, 29.02, 29.21, 31.65, 40.22,
40.29, 47.98, 61.26, 62.56, 67.76. 31P NMR (160 MHz,
CD3COCD3, ppm): 1.75 (s). Yield: 93.7% w/w. AgNO3 test:
positive but with negligible quantities of AgCl.
DOI: 10.1021/acs.iecr.7b04147
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[TOMA] [BA]. 1H NMR (400 MHz, CD3COCD3, ppm):
0.85−0.90 (m, 12H, 4CH3), 1.20−1.40 (m, 44H, CH2), 1.60−
1.75 (m, 6H, 3CH2), 3.34 (s, 3H, N−CH3), 3.54−3.62 (m, 6H,
3N−CH2), 7.20−7.25 (m, 3H), 8.00−8.10 (m, 2H). 13C NMR
(100 MHz, CD3COCD3, ppm): 13.49, 22.41, 28.61, 28.80,
28.96, 29.00, 29.19, 29.38, 31.61, 47.82, 61.06, 126.62, 127.86,
129.45, 142.05, 169.31. Yield: 84.7% w/w. AgNO3 test:
negative.
[P6,6,6,14] [BA]. 1H NMR (400 MHz, CD3COCD3, ppm):
0.85−0.95 (m, 12H, 4CH3), 1.25−1.55 (m, 48H), 2.20−2.30
(m, 8H, 4PCH2), 7.15−7.20 (m, 3H), 7.95−8.00 (m, 2H). 13C
NMR (100 MHz, CDCl3, ppm): 13.72, 13.80, 13.91, 18.49,
18.96, 21.52, 21.57, 22.123, 22.21, 22.48, 28.75, 29.10, 29.15,
29.33, 29.44, 29.47, 30.10, 30.25, 30.43, 30.57, 30.86, 31.11,
31.71, 127.08, 128.91, 129.25, 139.50, 171.48. 31P NMR (160
MHz, CD3COCD3, ppm): 33.26 (s). Yield: 84.3% w/w.
AgNO3 test: negative.
[P6,6,6,14] [D2EHP]. 1H NMR (400 MHz, CD3COCD3, ppm):
0.85−0.95 (m, 24H, 8CH3), 1.25−1.55 (m, 66H), 2.50−2.60
(m, 8H, 4PCH2), 3.80−3.85 (m, 4H, 2OCH2). 13C NMR (100
MHz, CD3COCD3, ppm): 10.58, 13.45, 13.59, 21.37, 22.23,
22.95, 23.33, 28.60, 28.79, 28.98, 29.18, 29.37, 29.49, 29.55,
30.13, 30.46, 30.96, 40.35, 40.43, 67.19, 67.25. 31P NMR (160
MHz, CD3COCD3, ppm): 1.89 (s), 33.29 (s). Yield: 90.7% w/
w. AgNO3 test: positive but with negligible quantities of AgCl.
Figure 1 shows the structure of the synthesized TSILs which
exhibit two important characteristics. First, the cations
Figure 1. Molecular structure of the corresponding cations and anions
of the TSILs used in this work: (a) trioctylmethylammonium
[TOMA]+; b) trihexyltetradecylphosphonium [P6,6,6,14]+; (c) bis(2-
ethylhexyl) phosphate [D2EHP]−; and (d) benzoate [BA]−.
[TOMA]+ and [P6,6,6,14]+ (see Figure 1a,b) are aliphatic as
they contained long alkyl chains providing good hydro-
phobicity. Second, the anion [D2EHP]− was synthesized
from the organic extractant bis(2-ethylhexyl) phosphoric acid
(D2EHPA) which represented a suitable extractant for
Mo(VI)3. This last structure, described in Figure 1c, showed
two parts: the two aliphatic chains and a coordinating group
corresponding to the phosphate. On the other hand, the anion
[BA]− (see Figure 1d) was selected because this molecule also
showed a hydrophobic part given by the benzene group and the
coordinating part provided by the carboxylate group.
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2.3. Solvent Extraction Experiments. Solvent extraction
experiments were carried out at 293 K, measured with a
thermocouple with a resolution of 0.1 K, in an open flask where
2 mL of aqueous solution containing Mo(VI) and 2 mL of the
organic phase were mixed and stirred for 40 min to reach the
equilibrium condition. After that, another 40 min of
centrifugation was required to achieve a complete phase
splitting. All the SX experiments were carried out in duplicate.
The concentration of the remaining Mo(VI) in the aqueous
phase was quantified by AAS. The concentration of
molybdenum in the organic phase was determined through a
mass balance. Simultaneously, the initial and the equilibrium
pH were measured during each of the SX tests. The solvent
extraction performance can be quantified through the
extraction percentage and the distribution coefficient as follows:
D
%E =
D + Vaq /Vorg (1)
[Mo]org
D=
[Mo]aq (2)
where Vorg and Vaq are the volume of the organic and aqueous
phases, respectively. Finally, after the extraction assays, the
stripping of molybdenum from the loaded phase was carried
out by stirring the organic phase and the stripping solution of
ammonium carbonate in an open flask for 40 min. The final
concentration of Mo(VI) in the stripping solution was
determined by AAS.
3. RESULTS AND DISCUSSION
3.1. Effect of the Initial pH on the Extraction
Percentage. A leaching of the molybdenite generates an
acid solution of Mo(VI) with pH values between 0 and 0.52
where, mostly, the MoO2+ 2 cation is present in aqueous
solution,42−44 and it can be extracted to different extents
depending on the pH value. Figure 2 shows the extraction
percentage of Mo(VI) as a function of the initial pH when the
TSILs [TOMA][D2EHP] and [TOMA][BA] were used as
extractants and kerosene used as the diluent.
It can be observed that both TSILs allowed the obtaining of
high extraction percentages in the whole range of initial pHs.
Figure 2. Extraction percentage of Mo(VI) as a function of the initial
pH using two different TSILs as the extractants and kerosene as the
diluent. Initial concentration of Mo(VI) in the aqueous phase was
equal to 1.0 g/L. Maximum uncertainties are ±0.7% for [TOMA]-
[D2EHP] and ±0.2% for [TOMA][BA] with 95% confidence level.
DOI: 10.1021/acs.iecr.7b04147
Ind. Eng. Chem. Res. 2018, 57, 1621−1629
Industrial & Engineering Chemistry Research
Figure 3. Effect of the cation, the anion, and the diluent on the extraction percentage. Initial concentration of Mo(VI) = 1 g/L, initial pH 1, and the
extractant concentration 1% v/v. Maximum uncertainty ±11% with a confidence level of 95%.
Nevertheless, the extractions improved when the initial pH was
nearly at a value of 1 for both tested extractants. However, the
difference between the extraction percentages obtained with
both extractants can be considered negligible in the studied pH
range. In spite of this, [TOMA][BA] showed better extractions
than [TOMA][D2EHP].
3.2. Effect of the Cation and the Anion on the
Extraction Percentage. In the previous results, it was
observed that the anion [BA]− showed the best values of
extraction percentages. In Figure 3 the effect of the anion and
the cation of the extractant on the extraction percentage can be
analyzed. Furthermore, the effect of the three different diluents
on the extraction percentage can be assessed in the same figure.
The results reported in Figure 3 show that high extraction
performances were observed for all the synthesized ionic liquids
showing high ability to extract molybdenum. Therefore, these
TSILs could be promising extractants for future industrial
applications.
On the other hand, when kerosene was used as the diluent,
all the extractants showed the highest extraction percentages
with negligible differences between them. Next, when kerosene
is replaced with the ionic liquid [omim][Tf2N], the extraction
percentages decreased and the differences between the
performance of each extractant became more notorious. As
observed from the entire results reported in Figure 3, the best
extractant was [TOMA][BA] followed by [TOMA][D2EHP].
Therefore, the more favorable cation was [TOMA]+. On the
other hand, slightly lower extraction percentages were obtained
with phosphonium ionic liquids when compared to ammonium
ones, where the anion [BA]− showed the highest extraction
percentages. Finally, when using [bmim][Tf2N] as the diluent,
more marked differences between the TSILs could be observed
where the best extraction percentages corresponded to the
extractant [TOMA][D2EHP] and no extraction was obtained
with [TOMA][BA]. The same trend was observed for the
cation [P6,6,6,14]+ where [D2EHP]− showed better results than
[BA]−. Thus, in order of extraction percentages, [TOMA]+ >
[P6,6,6,14]+ and [BA]− > [D2EHP]−, except for the diluent
[bmim][Tf2N] where [D2EHP]− > [BA]−. Although the
ammonium-based TSILs showed the best extraction perform-
ances, when selecting an extractant for a hydrometallurgical
process, other technical considerations should be taken into
account, for instance, viscosity and interfacial tension.
3.3. Effect of the Diluent on the Extraction Percent-
age. A second examination of the results reported in Figure 3
indicates that when the diluent is replaced from kerosene to the
ionic liquids, a marked decrease in the extraction percentage
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was observed. Hence, the diluent exhibited a strong effect on
the extraction percentage because of the interaction between
the extractant and the diluent. In the first case, the diluent was
kerosene which is mainly a mixture of several aliphatic
compounds. This diluent could exhibit a weak interaction
with a more polar compound such as a TSIL. In the second
case, the diluent [omim][Tf2N] shows more polar behavior
than kerosene. Then there would have been a stronger
interaction between the extractant and the diluent, decreasing
the extraction percentage. Finally, the diluent [bmim][Tf2N]
was even more polar than [omim][Tf2N] due to the short
aliphatic chain of the [bmim]+ cation. This resulted in a very
strong affinity between the extractant and the diluent that could
be observed through the significant decrease in the extraction
percentage in Figure 3.
To provide a better understanding about these interaction
effects between extractant and diluents, COSMO-RS calcu-
lations (Conductor Like Screening Model for Real Solvents)
were performed to obtain the density charge distribution
around these molecules to quantify how polar they are by
means of the σ-profiles.45 The calculations were performed
using COSMOThermX software version C30_1601. The peaks
presented in the σ-profiles plots allowed the identification of
whether a chemical species was either polar or nonpolar. If the
peak was tall, narrow, and located in the center of the
chromatogram, then the compound was nonpolar because the
same density charge distribution was found along the molecule.
However, if a molecule showed two peaks far from the center of
the diagram, then it was a polar molecule.46 Figure 4 depicts the
σ-profiles for the system [TOMA][BA]−kerosene and Figure 5
Figure 4. σ-Profiles for the system [TOMA][BA]−kerosene.
DOI: 10.1021/acs.iecr.7b04147
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shows the σ-profiles for the system [TOMA][BA]−[omim]- Table 1. Water Content of the Extractant Solutions
[Tf2N] to describe the interaction between the extractant and Measured before and after the Extraction Process for 1.4%
the diluent. (v/v) of Extractanta
extractant solution sample water content (% v/v)
kerosene−[TOMA][D2EHP] before 0.02 ± 0.0008
after 0.16 ± 0.003
[bmim][Tf2N]−[TOMA][D2EHP] before 0.06 ± 0.001
after 1.28 ± 0.03
a
Uncertainties are expressed with a confidence level of 95%.

can be considered hydrophobic and the water coextraction

Figure 5. σ-Profiles for the system [TOMA][BA]−[omim][Tf2N].
In Figure 4 the σ-profiles of n-decane were taken as a
representative molecule for kerosene which is a mixture of
aliphatic compounds (C6−C16). This profile exhibited a tall
peak near the center of the diagram (−0.001 e/A2), showing
the highly nonpolar nature of this molecule. The ionic liquid
[TOMA][BA], though, showed two peaks: a tall peak around
−0.002 e/A2, corresponding to the positive charge of the
cation; and a little peak near 0.006 e/A2, corresponding to the
benzoate anion. To have a high interaction and thus a decrease
in the extraction performance, two molecules should exhibit the
same peaks but with opposite signs, and this was not the case.
Therefore, the slight interaction between [TOMA][BA] and n-
decane can explain these high extraction percentages.
In Figure 5 it can be observed that the ionic liquid
[omim][Tf2N] shows two distinct peaks: one at −0.002 e/A2,
corresponding to the [omim]+; and the other at 0.011 e/A2 of
[Tf2N]−. In this case, a stronger interaction could be predicted
than the previous case because the peaks of the [Tf2N]− and
the peak of [TOMA]+ are of similar value. However, the peak
of [omim]+ was not similar to [BA]−, allowing for high
extraction percentages.
Finally, when the ionic liquid [omim][Tf2N] was replaced
with [bmim][Tf2N] as the diluent, more interaction between
this and [TOMA][BA] was expected because the [bmim]+
provided more polarity than [omim]+, resulting in a strong
affinity with the [BA]− and thus a decrease in the extraction
percentage.
3.4. Solubility of Water in the Synthesized Ionic
Liquids. The hydrophobic character of the synthesized ionic
liquids was tested by means of additional solvent extraction
experiments. Table 1 reports these results, which summarize
the water content quantified in each organic phase before and
after extraction.
From the results shown in Table 1, it can be observed that
the initial water content of both samples was quite low and this
percentage slightly increased after the solvent extraction
experiments. The hydrophobic nature of kerosene was noticed
in Table 1 with the lowest water content before and after the
extractions. In this extractant solution, kerosene was the major
component explaining the marginally higher water content after
the extraction. In the second solution, a slightly higher water
content was measured after the extraction. Nevertheless, the
water absorption in the ionic liquid phase was low; the system
1625
should not affect the extraction performance of Mo(VI).
3.5. Solvent Extraction Mechanism. Several studies have
proposed the extraction stoichiometry when ammonium-based
ionic liquids were used as extractant in metal extraction
processes. In those studies, a solvation mechanism was reported
when the ionic liquids were diluted in molecular diluents.32,35,38
However, the equilibrium pH of those works was around a
value of 4. In this study, the initial pH was around a value of 0.5
to ensure the extraction of the MoO2+ 2 cation. At this low pH
value, the ionic liquid extractant could undergo splitting
forming the [TOMA]2SO4 and HBA species where the organic
acid extracts Mo(VI). Therefore, a reasonable extraction
mechanism for the ionic liquids used in this work, when
diluted in kerosene, is
+ −
MoO22(aq) + 2[TOMA][BA](org) + SO24(aq)
⇌ MoO2 ·BA 2(org) + [TOMA]2 SO4(org)
(3)
The experimental determination of the proposed stoichiom-
etry involves the slope analysis where the distribution
coefficient and the extraction equilibrium constant can be
estimated by means of eqs 4 and 5, respectively:
[MoO2 ·BA 2(org)]
D=
[MoO22 +](aq) (4)
D[[TOMA]2 SO4(org)]
Kex =
[SO24 −]·[[TOMA][BA]]2 (5)
log D = 2 log[TOMA][BA] + log[SO24 −] + log Kex
− log[TOMA]2 SO2 (6)
Therefore, to demonstrate this extraction mechanism, a slope
with a value of 2 should be obtained when plotting the
distribution coefficient as a function of the concentration of the
TSIL at equilibrium. Figure 6 shows the slope analysis when the
extractant solution was [TOMA][BA]−kerosene.
It can be observed in Figure 6 that the slope of the linear
regression was close to 2.0, demonstrating the proposed
extraction mechanism. In addition to this, the equilibrium pH is
higher than the initial pH, a demonstration of the fact that
[TOMA][BA] extracts acid prior to the extraction of Mo(VI).
The next step considers the use of the ionic liquid
[omim][Tf2N] as the diluent. Recent studies38,47 have
demonstrated that the extraction with ammonium-based ionic
liquids of acidic extractants diluted in another ionic liquid as
diluent, at low pH values, occurs in two steps. First, the cation
extracts the mineral acid into the extractant phase, and second,
the anion reacts with protons to produce the organic acid
which, in turn, is a cationic extractant. Therefore, considering
DOI: 10.1021/acs.iecr.7b04147
Ind. Eng. Chem. Res. 2018, 57, 1621−1629
Industrial & Engineering Chemistry Research
Figure 6. Linear representation of eq 4 to verify the extraction
stoichiometry of Mo(VI) as a function of the concentration of
[TOMA][BA] at equilibrium. Initial [Mo(VI)] = 0.83 g/L; initial pH
0.65; average equilibrium pH 0.74. Maximum uncertainty of [Mo(VI)]
at equilibrium ±0.07 g/L with a confidence level of 95%.
this last mechanism, the extraction of Mo(VI) in sulfuric acid
media could occur as follows:
+ −
2[TOMA][BA](org) + 2H(aq) + SO24(aq)
⇌ [TOMA]2 SO4(org) + 2HBA (org) (7)
+ +
MoO22(aq) + 2HBA (org) ⇌ MoO2 ·BA 2(org) + 2H(aq) (8)
These two equilibrium reaction steps result in the following
overall equilibrium reaction for the extraction of Mo(VI):
+ −
MoO22(aq) + 2[TOMA][BA](org) + SO24(aq)
⇌ MoO2 ·BA 2(org) + [TOMA]2 SO4(org) (9)
Therefore, the slope analysis for this stoichiometry results in
log D = 2 log[TOMA][BA] + log[SO24 −] + log Kex
− log[TOMA]2 SO2 (10)
Equation 10 suggests that when plotting log D as a function of
log[TOMA][BA], with an increasing extractant concentration,
the slope of the experimental points should be 2.
On the other hand, [omim][Tf2N] should not appear in the
equilibrium equations since this ionic liquid does not have the
ability to coordinate metal ions.26,31 Figure 7 shows the slope
analysis when the ionic liquid [TOMA][BA] is the extractant.
In Figure 7, it is noted that the slope of the linear regression
was slightly higher than the expected value of 2. Therefore, with
these results, the proposed extraction mechanism given by eq 9
was corroborated. However, this slightly higher value in the
slope proposes that the organic acid, HBA, formed in the first
step of the extraction mechanism, could also be extracting
Mo(VI) to some extent. To corroborate this affirmation,
additional solvent extraction experiments, using HBA solely as
the extractant diluted in [omim][Tf2N], were carried out.
Figure 8 shows the log D as a function of log[HBA] for the
extraction of Mo(VI).
It can be observed that the slope of the linear regression
resulted in a value around 0.6, indicating that there is a
synergistic extraction between the ionic liquid extractant
[TOMA][BA] and the formed benzoic acid in the second
step of the equilibrium reaction. This is beneficial for the
1626
Article
Figure 7. Linear representation of eq 9 to verify the extraction
stoichiometry of Mo(VI) as a function of the concentration of
[TOMA][BA] at equilibrium when [omim][Tf2N] was the diluent.
Initial [Mo] = 1.0 g/L; initial pH 0.7. Maximum uncertainty of
[Mo(VI)] at equilibrium ±0.02 g/L with a confidence level of 95%.
Figure 8. Linear representation of eq 8 to verify the extraction
stoichiometry of Mo(VI) as a function of the concentration of
[omim][Tf2N] at equilibrium. Initial [Mo] = 1.0 g/L; initial pH 0.85.
Maximum uncertainty of [Mo(VI)] at equilibrium ±0.04 g/L with a
confidence level of 95%.
solvent extraction of Mo(VI) from aqueous solutions. Finally, it
is important to notice that when only 2% v/v of [TOMA][BA]
is used in [omim][Tf2N], it is possible to achieve an extraction
percentage of 93%; this is very promising for the use of these
kinds of ionic liquids in future industrial applications.
Another important point in this extraction mechanism is the
consumption of sulfate ions. To corroborate this, measure-
ments of sulfate concentration at equilibrium were performed
using UV−vis analysis. Results are shown in Table 2 and
reported as extraction percentage (%E). Also in this table, the
measured equilibrium pH values for the overall extraction
reaction (eq 9) are reported.
It can be observed that there is an extraction of sulfate ions
by [TOMA][BA] from the aqueous solution. This also
corroborates the proposed extraction mechanism. In addition
to this, a decrease in the equilibrium pH with regards to the
initial pH was observed. This is because the second extraction
step (eq 8) involves the extraction of Mo(VI) by HBA which,
in turn, is a cationic extractant releasing protons to the aqueous
phase. It was demonstrated above that the HBA formed in the
second extraction step also extracts Mo(VI) to some extent,
decreasing the pH of the aqueous phase. It is worth noting that
DOI: 10.1021/acs.iecr.7b04147
Ind. Eng. Chem. Res. 2018, 57, 1621−1629
Industrial & Engineering Chemistry Research Article

Table 2. Extraction Percentages (%E) of Sulfate Ions ionic [omim][Tf2N] the extractions were lower than when
Corresponding to eq 9 and the Equilibrium pH (pHeq) as a kerosene was the diluent, also via solvation. However, in this
Function of the Extractant Concentrationa case, the interaction between ionic liquid−ionic liquid is
stronger than the previous case. Therefore, the solvation is less
[TOMA][BA] (% v/v) %E[SO42−]eq pHeq favorable and then the stripping was easier. As a conclusion,
0.38 12.5 ± 8.9 0.62 ± 0.01 high extraction percentages in the SX stage result in poor
0.70 19.6 ± 10.1 0.62 ± 0.0 stripping performances. This conclusion could provide new
1.06 24.3 ± 7.4 0.58 ± 0.02 insights on the design of ionic liquids as extractants and as
1.41 22.0 ± 8.3 0.63 ± 0.02 diluents for an optimal metal extraction−stripping by knowing
1.79 23.9 ± 6.5 0.61 ± 0.02 only the extraction mechanism and the interaction extractant−
2.14 22.6 ± 4.6 0.59 ± 0.0 diluent.
a
Initial pH 0.7. Uncertainties are expressed with a level of confidence
of 95%. 4. CONCLUSIONS
the extraction mechanism for [TOMA][D2EHP] was not Solvent extraction of Mo(VI) was investigated using synthe-
studied when [omim][Tf2N] was the diluent because the sized ammonium- and phosphonium-based TSILs as extrac-
extraction should follow the same mechanism as [TOMA]- tants and commercially available imidazolium-based ionic
[BA]. liquids as diluents.
3.6. Stripping of Mo(VI) from the Loaded Phase. The In general, the TSILs produced high extraction percentages
stripping of the molybdenum from the loaded phase was when these were diluted in kerosene and [omim][Tf2N]. Then
necessary as the final step of the solvent extraction process. when the extraction capacities of the tested TSILs were
This stripping step was performed with solutions of ammonium compared, the best performances were observed for the cation
carbonate 1[M]. Figure 9 summarizes the stripping percentages [TOMA]+ and the anion [BA]− when kerosene and [omim]-
from the loaded phase. [Tf2N] were the diluents, and for the anion [D2EHP]− when
[bmim][Tf2N] was the diluent. Furthermore, the selection of
the diluent showed a significant influence on the solvent
extraction performance.
From the experiments carried out to establish the extraction
stoichiometry, it was found that when having an ionic liquid as
extractant diluted in kerosene or [omim][Tf2N], the extraction
process followed ion-exchange mechanism. On the other hand,
the stripping was carried out with a solution of ammonium
carbonate 1[M] and the extent of recovery of Mo(VI) in the
stripping process also depended on the diluent selected in the
solvent extraction step.
Finally, this work provides new insights on the use and
selection of ionic liquids as extractants and diluents for the
recovery of metal ions in hydrometallurgy.

■
*
ASSOCIATED CONTENT
S Supporting Information

Figure 9. Stripping performance of the Mo(VI) from the loaded phase The Supporting Information is available free of charge on the
using 1[M] of (NH4)2CO3. Maximum uncertainty ±28.7% with a ACS Publications website at DOI: 10.1021/acs.iecr.7b04147.
confidence level of 95%. Additional tabular data supporting Figures 2, 3, 6, 7, 8,
and 9 and Table 1 (PDF)

■
Figure 9 shows the stripping percentages of Mo(VI) from the
loaded extracting phase. In general, these organometallic
complexes are stable in acidic conditions. Therefore, the AUTHOR INFORMATION
application of a basic solution would make the complex Corresponding Author
unstable to finally release the Mo(VI) to the stripping solution. *Phone: +56 22 7181838. E-mail: esteban.quijada@usach.cl.
Moreover, this figure shows a very low molybdenum
recovery when kerosene was used as the diluent. As shown ORCID
above, the selection of the diluent plays an important role in the Esteban Quijada-Maldonado: 0000-0003-1411-4327
extraction percentage of Mo(VI). When kerosene was used as Notes
the diluent, very high extractions were obtained for all the The authors declare no competing financial interest.

extractants due to the low interaction kerosene−ionic liquid.
Furthermore, it was experimentally demonstrated that Mo(VI)
was extracted via solvation by ionic liquids. Therefore, because
of low interaction kerosene−extractant, the solvation is
favorable and a difficult stripping was observed.
On the other hand, better stripping percentages were
observed when the diluents were the ionic liquids. With the
1627
■
ACKNOWLEDGMENTS
Financial support from Project PAI 79140047 (CONICYT
Chile) and Project RC-130006-CILIS, granted by Fondo de
Innovación para la Competitividad del Ministerio de Economia,́
Fomento y Turismo, Chile, is kindly acknowledged.
DOI: 10.1021/acs.iecr.7b04147
Ind. Eng. Chem. Res. 2018, 57, 1621−1629
Industrial & Engineering Chemistry Research
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1629 DOI: 10.1021/acs.iecr.7b04147

Ind. Eng. Chem. Res. 2018, 57, 1621−1629