Dairo E Chaverra1,2, Oscar J Restrepo-Baena1, María C Ruiz2. 1. Department of Materials and Minerals, School of Mines, Universidad Nacional de Colombia, Calle 59A No. 63-20 Bloque 54, Medellín 050034, Colombia. 2. Department of Metallurgical Engineering, University of Concepcion, Edmundo Larenas 285, Concepción 3349001, Chile.
Abstract
The application of phosphonium-based ionic liquids (ILs) on the selective extraction of cobalt is presented. The extraction mechanism is established, and different parameters of the process are evaluated. It has been found that it is possible to extract cobalt from aqueous solutions in sulfate media, with the addition of sodium chloride, using phosphonium ILs. The cobalt extraction was selective with respect to nickel and strongly dependent on the chloride concentration in the aqueous solution. The cobalt extraction is given by an anion exchange mechanism through an endothermic process. Cobalt extractions greater than 98% were obtained using the proposed methods. Cobalt stripping from the loaded IL phase using water was proved. Therefore, an alternative extraction process to traditional organic solvents is proposed. This alternative has additional advantages such as easy handling, lower costs in reagents and equipment, and risk reduction.
The application of phosphonium-based ionic liquids (ILs) on the selective extraction of cobalt is presented. The extraction mechanism is established, and different parameters of the process are evaluated. It has been found that it is possible to extract cobalt from aqueous solutions in sulfate media, with the addition of sodium chloride, using phosphonium ILs. The cobalt extraction was selective with respect to nickel and strongly dependent on the chloride concentration in the aqueous solution. The cobalt extraction is given by an anion exchange mechanism through an endothermic process. Cobalt extractions greater than 98% were obtained using the proposed methods. Cobalt stripping from the loaded IL phase using water was proved. Therefore, an alternative extraction process to traditional organic solvents is proposed. This alternative has additional advantages such as easy handling, lower costs in reagents and equipment, and risk reduction.
The
metal processing industry
faces critical environmental and economic issues, such as low-concentration
metal ores and an increase in the demand for strategic metals, as
well as the protection of the environment, reduction in the use of
natural resources, and so forth.[1,2] In turn, cobalt is a
metal, which is used in many commercial, industrial, and military
applications, many of which are strategic and critical.Acidic
solutions that come from the leaching of lateritic nickel minerals,
dissolution of metal-rich mattes, or recycling processes are processed
in the cobalt and nickel metallurgy. These solutions contain different
metallic species, and their separation is a highly challenging problem.[3,4] Traditionally, cobalt and nickel are separated by selective oxidation
and precipitation processes which have low efficiency and low selectivity.[5] Extraction by solvents as a final stage to separate
the cobalt selectively and with high yields is also used. Organic
reagents such as Versatic 10 and LIX63,[6] Cyanex,[7,8] D2EHPA and LIX63,[9,10] Cyanex
272–Cyphos IL 101,[11,12] PRIMENE JMT-Cyanex
272,[13] mixture of PRIMENE JMT-Versatic
10,[14] and extractants derived from D2EHPA[15] have been studied. However, the volatility and
flammability of traditional organic solvents usually represent technical
problems and risks to the environment and human health.In recent
years, ionic liquids (ILs) have been accepted as an important family
of chemical compounds, which have been used for the purpose of both
organic diluents and extractive agents instead of traditional or commercial
uses. ILs are organic salts or eutectic mixtures of organic and inorganic
salts with a melting point below 100 °C. ILs have a structure
composed of an organic cation and a polyatomic organic or inorganic
anion. Their unique physicochemical properties, such as very high
flash point, negligible vapor pressure, high thermal stability, and
ability to adjust properties, have led them to an increase in interest
for different applications.[16−18] ILs play an active role in the
process of partitioning metal ions,
with exchange of a metal complex for an ionic or cationic constituent
of the IL, which represent an important mode of ionic transfer.[19] ILs could be used to extract metal ions from
an aqueous solution phase with relatively high efficiency in a short
period of time.[20] For example, Visser et
al.[21] designed a series of task-specific
ILs based on imidazole for the Hg(II) and Cd(II) extraction. The Nd(III)
extraction with 1-hexyl-3-methylimidazolium bis(2-ethylhexyl)phosphate,
[C6mim][DEHP], 1-hexyl-1-methylpyrrolidinium bis(2-ethylhexyl)phosphate,
[C6mpyr][DEHP], and tetrabutylammonium bis(2-ethylhexyl)phosphate,
[N4444][DEHP], were also studied.[22] An aqueous two-phase system formed by tetrabutylphosphonium nitrate,
[P4444][NO3], was developed for the selective
separation of Nd(III) from Co(II) and Ni(II).[23] Novel thiosalicylate-based ILs were synthesized and investigated
for Cu(II), Zn(II), and Cd(II) extraction.[24] Extraction and separation of Pt(IV), Pd(II), Ru(III), and Rh(III)
with imidazolium-based ILs were evaluated.[25] The mostly studied ILs for the extraction of metal ions are those
of imidazolium derivatives with different extractants, ligands, and
metal chelators.[7−9,26−33] However, they present two great disadvantages
that cannot be overcome in metal extraction. First, these are hydrolyzed
in an acid medium.[34,35] Second, many extraction mechanisms
are cation exchange[36,37] or anion exchange,[38,39] which indicates the release of 1-alkyl-3-methyl-imidazolium cations,
Cmim+, and bis(trifluoromethanesulfonyl)imide
anions, Tf2N–, to the aqueous phase.[40] These compounds can become persistent pollutants
in wastewater because of their high stability in water.[41]Phosphonium salts constitute an important
subclass of ILs, which are known to have important properties, sometimes
superior in comparison with those of the widely investigated nitrogen-based
ILs.[42] Some detailed studies about the
synthesis, physicochemical, and thermal properties of tetraalkylphosphonium
chlorides have been recently published.[43,44] Phosphonium
ILs, compared to 1,3-dialkylimidazolium salts, offer important advantages
in applications such as their low cost of preparation and low potential
for interaction with various solutes.[45] The extraction of different metallic species with these ILs has
been reported: extraction, separation, and recovery of Mo(VI) with
Cyphos IL 102,[46] Pd(II) extraction with
Cyphos IL 101 and Cyphos IL 104,[47−49] separation of Fe(III)
from Ni(II) with Cyphos IL
101,[50] U(VI) extraction with Cyphos IL
101,[51] extraction of Eu(III) and other
rare-earth elements with trihexyl(tetradecyl)phosphonium N,N,N′,N′-tetra(2-ethyl-hexyl)malonate, [P66614][MA], diluted
in trihexyl(tetradecyl)phosphonium nitrate, [P66614][NO3],[52] Rh(III) and Ru(III) extraction
with Cyphos IL 101 and Cyphos IL 104,[53] and extraction of Pt(IV), Pd(II), and Rh(III) with trioctyl(dodecyl)phosphoniumchloride, [P88812][Cl].[54]Regarding the use of ILs for the Co(II) extraction, there are several
studies: Co(II) extraction with Cyphos IL 101,[1,55−57] Cyphos IL 102,[56] Cyphos
IL 104,[1] Cyphos
IL 167,[56] trihexyl(tetradecyl)phosphoniumdicyanamide, [P66614][DCA],[58] tetraoctylphosphonium bromide, [P8888][Br],[56] and tetraoctylphosphonium oleate, [P8888][Oleate].[59] These investigations basically
show the effectiveness of ILs to extract mainly Co(II) and study the
dependence of variables such as IL concentration, pH, and acid concentration
in the aqueous solution.This paper aimed to study the cobalt
extraction from sulfate/chloride media by solvent extraction with
different ILs with trioctyl(alkyl)phosphonium cation, P888+, for the first time, as a contribution
to knowledge about the use of quaternary phosphonium salts in metal
extraction. They are compared with commercial ILs such as tricaprylmethylammonium
chloride, A336, and trihexyl(tetradecyl)phosphonium chloride, [P66614][Cl].
Materials
and Methods
Chemicals
For the preparation of
aqueous solutions, the following salts were
purchased from Merck: CoSO4·7H2O, NiSO4·6H2O, and NaCl. Aqueous solutions at different
concentrations of chloride and sulfuric acid were prepared in Milli-Q
water (Milli-Q Direct). The concentration of chloride in the aqueous
solutions was achieved by adding NaCl or HCl. The A336 and [P66614][Cl] ILs were purchased from Sigma-Aldrich. Toluene purchased
from Merck was used for the dilution of the ILs.
Experimental Apparatus and Procedures
The hydrophobic
[P888][Cl] ILs were
studied in cobalt and nickel extraction. Their structure is shown
in Figure . They were
synthesized by the addition of trioctylphosphine to chloroalkanes
according to the proposal by Bradaric et al.[60] A description of the synthesis is presented in the Supporting Information file.
Figure 1
Structure of trioctyl(alkyl)phosphonium
chloride
ILs, where n = 5, 8, 14, and 16 were investigated.
Structure of trioctyl(alkyl)phosphoniumchloride
ILs, where n = 5, 8, 14, and 16 were investigated.
Extraction
and Stripping Processes
The
extraction experiments were carried out in a 50 mL double-jacketed
glass reactor with a hot water flow from a PolyScience thermostatic
bath. The water flow allowed maintaining a constant temperature during
the contact of both phases. The reactor was placed on a plate with
magnetic stirring. The experiments were performed at 1200 rpm and
25 °C by mixing 1 mL of pure IL and 2 mL of aqueous solution.
Phase separation which took less than 2 min to complete was carried
out in glass separatory funnels. The determination coefficient determination
and extraction percentage were calculated according to eqs and 2, respectively.where [Mz+] is the concentration of the metal ion in the
aqueous phase, A, and the IL. The subscripts “in” and
“eq” refer to the initial and equilibrium concentration
of the metal ion, respectively. The metal concentration in the IL
phase was calculated as the difference between the initial and equilibrium
concentration in the aqueous phase. The stripping was carried out
in the same reactor. The loaded IL (1 mL) from 3 M HCl and 1 g/L Co(II)
aqueous solution was mixed with 2 mL of different aqueous solutions
(pure H2O, 0.1 M and 0.2 M HCl, and 0.2 M H2SO4) at 25 °C within 20 min. The stripping percentage
was calculated according to eq .where [Mz+] is the concentration
of the metal ion in the stripping phase, st, and the IL and V is the volume of the stripping phase, st, and the IL.
Chemical Composition
of the Aqueous Solution Measurement
Co(II) and Ni(II) concentrations
in the aqueous solutions were measured by mean of an Agilent 200 series
AA spectrometer. The metal concentration in the aqueous solution was
measured before and after contact with the ILs. For solutions with
only cobalt content, its concentration was measured by volumetric
titration using ethylenediaminetetraacetic acid (EDTA). An aliquot
of 1.6 mL of aqueous solution was taken and diluted to 10 mL using
deionized water. Two aliquots of 4 mL were taken and titrated with
EDTA using murexide as indicator. This method was previously standardized
using a 1000 mg/L Co(II) standard solution where a maximum relative
deviation of 1% was obtained.
Viscosity
Measurement
The viscosity was measured with
a ViscoSystem AVS 370 viscometer controlled by the WinVisco 370 software
using # 200 and 450 Cannon-Fenske Routine Capillaries. The viscosity
measurements were made by the pressure method. The parameters included
in the software were a preheating time of 15 min, five measurements,
and a maximum relative deviation of 1%.
UV/Vis
Spectroscopy
The UV/vis
OPTIZEN POP spectrophotometer was used using optical polystyrene cuvettes
(Deltalab) with an optical path (metric) of 10 mm, having a capacity
of 1.5 mL. The UV/vis absorption spectra were recorded in a range
of 350–750 nm. As a blank, ultrapure water and pure ILs were
used.
Results
and Discussion
In most industrial processes for obtaining
nickel and cobalt, aqueous solutions of sulfuric acid are used as
a leaching agent. This is mainly
seen when nickel and cobalt are primarily obtained from the ores of
nickel sulfides and nickel laterites. Also, studies with phosphoniumsalts have shown that it is possible to extract Co(II) ions from chloride
media. With this in mind, [P888][Cl]
ILs were studied and compared with A336 and [P66614][Cl]
ILs in the Co(II) extraction from aqueous solutions of sulfate media
with the addition of chloride ions. The selectivity for the Co(II)
extraction with respect to Ni(II), time, concentration of reagents,
extraction mechanism, and temperature was evaluated.
Selectivity
in the Extraction of Cobalt versus
Nickel
Co(II) and Ni(II) extraction experiments were performed
in an aqueous solution of 1 g/L of Co(II) and 1 g/L of Ni(II), 1 M
H2SO4 (0.5 M for A336), and 2 M HCl and 5 M
HCl. The contact time of the phases was 20 min. The Ni(II) extraction
was negligible for all ILs. It will be shown that the ILs studied
extract the metallic species through an anion exchange, and as Ni(II)
does not form anionic complexes in sulfate and chloride media, it
is not possible to extract it with the ILs studied here. Table shows that the most
effective IL for the extraction of Co(II) is [P8888][Cl],
while A336 is the least effective. However, all the ILs were studied
in order to evaluate the effect of the parameters considered on cobalt
extraction.
Table 1
Co(II) and Ni(II) Extraction Percentage
with Several
ILsa
extraction (%)
[P8885][Cl]
[P8888][Cl]
[P88814][Cl]
[P88816][Cl]
A336
Co(II)
Ni(II)
Co(II)
Ni(II)
Co(II)
Ni(II)
Co(II)
Ni(II)
Co(II)
Ni(II)
2 M HCl
26.7
∼0
71.2
∼0
57.6
∼0
50.0
∼0
5.0
∼0
5 M HCl
89.8
98.3
96.6
95.8
78.8
Aqueous phase =
1 M H2SO4 (0.5
M for A336), 1 g/L of Co(II), 1 g/L of Ni(II). Equilibration time
= 20 min, temperature = 25 °C, A/O ratio = 2:1.
Aqueous phase =
1 M H2SO4 (0.5
M for A336), 1 g/L of Co(II), 1 g/L of Ni(II). Equilibration time
= 20 min, temperature = 25 °C, A/O ratio = 2:1.Table shows that pure water is the most effective
stripping phase. The
stripping percentage decreases with increasing chloride concentration
in the stripping phase. The discharge of H+ ions affects
the discharge of Co(II). Cobalt stripping in sulfuric acid solution
is less favorable in comparison with that in the other stripping solutions.
Table 2
Stripping Percentagesa
stripping solution
H2O
HCl (0.1 M)
HCl (0.2 M)
H2SO4 (0.2 M)
S (%)
100
99.4
97.7
93.6
Stripping phase = 2 mL, loaded IL =
1 mL. Contact time = 20 min, temperature = 25 °C.
Stripping phase = 2 mL, loaded IL =
1 mL. Contact time = 20 min, temperature = 25 °C.
Effect of Phase Contact
Time
Co(II) extraction experiments were carried out with
[P88814][Cl] and A336 at different contact times. An aqueous
solution of 0.5 M H2SO4, 3 M HCl, and 1 g/L
of Co(II) was used. The results are shown in Figure . For [P88814][Cl], the extraction
increases rapidly, having 50% extraction after 1 min of contact and
70% after 2 min, reaching equilibrium at 10 min of contact of both
phases. The extraction kinetics is slower for A336 reaching equilibrium
after 20 min. The constant rate was determined through the linear
adjustment of the initial extraction stage according to eq .where [Co2+]A,in and [Co2+]A,f refer to the Co(II)
concentrations (g/L) in the aqueous phase before and after the extraction,
respectively, k (min–1) is the
rate constant, and t (min) is the contact phase time.
A constant rate of 0.1043 min–1 was calculated for
A336, while for [P88814][Cl], it was 0.618 min–1. [P88814][Cl] shows a cobalt extraction rate considerably
higher than A336. In addition, [P88814][Cl] had a viscosity
of 49.79 mm2/s at 25 °C, much lower compared to the
value of 1152.86 mm2/s for A336. Hence, it is concluded
that the difference in viscosity between the two ILs is reflected
in the extraction rate. The viscosity of ILs can affect the diffusion
rate.
Figure 2
Effects
of contact time on Co(II) extraction with the [P88814][Cl]
and A336 ILs. Aqueous phase = 0.5 M H2SO4, 3
M HCl, and 1 g/L of Co(II). Temperature = 25 °C, A/O ratio =
2:1.
Effects
of contact time on Co(II) extraction with the [P88814][Cl]
and A336 ILs. Aqueous phase = 0.5 M H2SO4, 3
M HCl, and 1 g/L of Co(II). Temperature = 25 °C, A/O ratio =
2:1.
Effect
of
Chloride Concentration
Extraction tests were carried out
for different concentrations of chloride, with an initial concentration
of 1 g/L of Co(II) and 0.5 M H2SO4. It is observed
in Figure how the
Co(II) extraction depends strongly on the initial concentration of
chloride in the aqueous solution for all ILs studied. The Co(II) extraction
is quite similar with the [P888][Cl]
IL extraction except that n = 5. The extraction with
the A336 IL is the lowest. The Co(II) extraction with the [P8888][Cl] IL seems to be slightly higher at low chloride concentrations.
The [P8888][Cl] IL is an interesting option to develop
the Co(II) extraction process, while A336 is not efficient for Co(II)
extraction because it needs high chloride acid concentrations.
Figure 3
Co(II) extraction
percentage as a function of
the initial concentration
of HCl in the aqueous solution. Aqueous phase = 0.5 M H2SO4 and 1 g/L of Co(II). Equilibration time = 20 min,
temperature = 25 °C, A/O ratio = 2:1.
Co(II) extraction
percentage as a function of
the initial concentration
of HCl in the aqueous solution. Aqueous phase = 0.5 M H2SO4 and 1 g/L of Co(II). Equilibration time = 20 min,
temperature = 25 °C, A/O ratio = 2:1.
Effect of Sulfuric Acid Concentration
The
extraction
of Co(II) from aqueous solutions of 1 M HCl, 3 M
HCl, and 3 M NaCl at different concentrations of H2SO4 and 1 g/L of Co(II) was studied. The extraction of Co(II)
was done with the [P88814][Cl] IL and compared with A336.In Figure , it
is observed that there is a linear dependence between the Co(II) extraction
and the concentration of H2SO4. For the extraction
with [P88814][Cl], the tendency to increase the Co(II)
extraction with the increase in the concentration of H2SO4 is similar at 1 M HCl, 3 M HCl, and 3 M NaCl media.
A linear dependence between the concentration of H2SO4 and Co(II) extraction from a 3 M HCl medium with the A336
IL was also found. The dependence of H2SO4 is
much more significant to the Co(II) extraction with the A336 IL compared
to that with [P88814][Cl]. Therefore, a lower concentration
of H2SO4 is required for ionic phosphonium liquids.
Figure 4
Effect
of the
initial
concentration of H2SO4 on the Co(II) extraction
with [P88814][Cl] (3 M NaCl, 3 M HCl, and 1 M HCl) and
A336 (3 M HCl). Aqueous phase = 1 g/L of Co(II). Equilibration time
= 20 min, temperature = 25 °C, A/O ratio = 2:1.
Effect
of the
initial
concentration of H2SO4 on the Co(II) extraction
with [P88814][Cl] (3 M NaCl, 3 M HCl, and 1 M HCl) and
A336 (3 M HCl). Aqueous phase = 1 g/L of Co(II). Equilibration time
= 20 min, temperature = 25 °C, A/O ratio = 2:1.
Extraction Mechanism
The UV/vis absorption
spectra shown in Figure for the [P88814][Cl] IL after
the Co(II) extraction from NaCl, HCl, and H2SO4 media exhibit an absorption band between 600 and 750 nm, which is
characteristic of the CoCl42– complex.[61] This suggests that the ILs solubilize the CoCl42– complex and release two chloride ions
to the aqueous phase in order to maintain the neutrality. This seems
to be true regardless of the matrix of the aqueous solution. One similar
spectrum was obtained for the A336 IL after the Co(II) extraction
from HCl media. Therefore, the Co(II) extraction begins in the aqueous
phase with the formation of the CoCl42– complex, which predominates as the chloride concentration increases.[62]
Figure 5
UV/vis absorption
spectra for the loaded [P88814][Cl] from aqueous solutions
of different matrices (NaCl, HCl, H2SO4) and
the loaded A336 from HCl.
UV/vis absorption
spectra for the loaded [P88814][Cl] from aqueous solutions
of different matrices (NaCl, HCl, H2SO4) and
the loaded A336 from HCl.The reaction of the Co(II) extraction
represented by an anion exchange according to eq is proposed. For each mole of the CoCl42– complex solubilized in the IL phase,
2 mol of chloride ions is exchanged. The formation of the CoCl42– complex is favored by the presence of
ions H+ and HSO4–, which allow
dehydration of the Co(II) ions.[63]The stoichiometry
in 5 was determined using the slope analysis
method. Neglecting the effects of nonlinearity, we have an approximation
to the equilibrium constant given by eq .Taking into account that the distribution coefficient
is given
by , replacing in eq and taking logarithm on both sides, eq is obtained.The [P8888][Cl] IL was diluted in toluene, and different concentrations were
obtained. Co(II) extraction experiments were carried out in 3 M NaCl
and 4 M NaCl solution. The initial concentration of Co(II) was 0.5
g/L. The slope analysis from Figure shows straight lines, as predicted by eq . Slope values of 1.75 and 1.79
were obtained for chloride concentrations of 3 and 4 M, respectively.
These values are close to 2, which confirm that the loaded IL phase
contains about 2 mol of IL per mole of extracted cobalt(II) ion according
to eq and also takes
into account the UV/vis results. For the plot of log D versus log[A336], a slope of 1.81 was obtained in 4 M NaCl media
(Figure S1). This suggests that the extraction
mechanism is similar to that found for phosphonium ILs. In addition,
the UV/vis spectra (Figure ) for the charged A336 IL show the presence of the CoCl42– complex.
Figure 6
Graph of log D vs log([P8888][Cl]) for slope analysis in the
Co(II) extraction from
3 M NaCl and 4 M NaCl aqueous solutions. Aqueous phase = 0.5 g/L Co(II).
Equilibration time = 20 min, temperature = 25 °C, A/O ratio =
2:1.
Graph of log D vs log([P8888][Cl]) for slope analysis in the
Co(II) extraction from
3 M NaCl and 4 M NaCl aqueous solutions. Aqueous phase = 0.5 g/L Co(II).
Equilibration time = 20 min, temperature = 25 °C, A/O ratio =
2:1.These experiments were
repeated in 4 M HCl media. A slope of 0.98 was obtained, which is
very far from 2 (Figure S2). In this case,
the presence of the H+ ions released by the HCl modifies
the extraction mechanism. A coextraction of HCl is proposed according
to the addition reaction given by eq . A slope of 0.79 was obtained for the plot of log D versus log(A336) when the Co(II) extraction was made from
a 4 M solution of HCl (Figure S1).The Co(II)
extraction with
the [P88814][Cl] IL from 5 M NaCl and 5 M HCl aqueous solutions,
both with 1 g/L of Co(II) and A/O = 1, was done. For the NaCl media,
a Co(II) extraction of 99.5% was obtained, while for the HCl media,
the Co(II) extraction was 98.1%. The [P88814][Cl] IL loaded
came in contact with deionized water (pH ≈ 6) at a 1/1 ratio.
For the [P88814][Cl] IL loaded from the NaCl media, the
discharge percentage was 98.3% with a final pH of the discharge solution
of 4.3. The decrease in pH of the water is due to the presence of
chloride ions which alter the activity of the water. For the [P88814][Cl] loaded from the HCl media, the discharge percentage
was 61.9% with a final pH of the discharge solution of 1.4. The decrease
in pH is due to the discharge of coextracted H+ ions. The
discharge of H+ ions affects the Co(II) stripping, being
only 61.9% compared to 98.3% for the case that H+ is not
present.
Effect
of System Temperature
The Co(II) concentration in the aqueous
phase was 1 g/L (0.017 M); therefore, it can be said that chloride
ions exist in large excess compared to Co(II) ions, so it is considered
that the total concentration of chloride ions is approximately constant.
At equilibrium, the change in Gibbs free energy associated with the
extraction reaction at a given temperature can be determined according
to eq .where R is the universal gas constant and T is the absolute temperature at which the extraction process
is carried out. The change of free energy is related to the changes
of enthalpy and entropy by eq .Equation is
derived from eqs and 10.Assuming
ΔH° and ΔS°
being very weak with the change in temperature, their values were
calculated from the slope and intercepts of the lines of the van’t
Hoff plot presented in Figure . The Co(II) extraction was carried out in an aqueous solution
of 3 M NaCl, 0.5 M H2SO4, and 1 g/L of Co(II).
The results are summarized in Table . An increase in the extraction of Co(II) was found
with the increase in the temperature of the extraction process. Positive
values for ΔH° indicate an endothermic
process. The endothermic process is also due to the need to break
the Co(II)–H2O bond of the cobalt hydration in the
aqueous solution. This implies that the formation of the complex is
thermodynamically unfavorable, which indicates that the formation
of the CoCl42– complex occurs mainly
at the interphase, accompanied by the dehydration of the metal center.
The increase in entropy after the dehydration of the metal center
drives the extraction. The high value of the extraction entropy could
be attributed to the loss of an organized aggregation structure within
the IL phase after the transfer of the CoCl42– complex between both
phases (Quinn et al., 2013). The negative value to the Gibbs free
energy change indicates that all the ILs studied are favorable for
the Co(II) extraction process.
Figure 7
Graph of log D vs 1000/T for the
Co(II) extraction with the [P888][Cl]
ILs (n = 8, 14, and 16), [P66614][Cl],
and A336. Aqueous phase = 0.5 M H2SO4, 3 M NaCl,
and 1 g/L of Co(II). Equilibration time = 20 min, A/O ratio = 2:1.
Table 3
Thermodynamic Parameters
for the Co(II) Extraction
IL
A336
[P8888][Cl]
[P88814][Cl]
[P88816][Cl]
[P66614][Cl]
ΔH° (kJ mol–1 K–1)
47.17
27.64
16.91
32.72
23.90
ΔS° (J mol–1 K–1)
163.96
120.69
74.11
128.73
107.38
ΔGex (kJ mol–1 K–1)
–1.72
–8.34
–5.19
–5.66
–8.12
Graph of log D vs 1000/T for the
Co(II) extraction with the [P888][Cl]
ILs (n = 8, 14, and 16), [P66614][Cl],
and A336. Aqueous phase = 0.5 M H2SO4, 3 M NaCl,
and 1 g/L of Co(II). Equilibration time = 20 min, A/O ratio = 2:1.The Co(II) extraction
has a linear
dependence with the process temperature (Figure S3). The increase is similar for the [P8888][Cl]
and [P88814][Cl] ILs where the slope of the trend line
is similar. There is an increase of 3.23% points in the Co(II) extraction
when passing from 298.15 to 318.15 K for the [P8888][Cl]
IL. There is a more significant temperature dependence for the [P88816][Cl] IL. In this case, the Co(II) extraction increased
in 8.56% points when the system temperature increased from 298.15
to 318.15 K. The extraction with the [P66614][Cl] IL was
compared. The behavior in the cobalt extraction with the temperature
change is practically the same compared to the [P8888][Cl]
IL. However, there is a great difference between their viscosities;
the viscosity of the [P66614][Cl] IL is 7 times higher
than the viscosity of the [P8888][Cl] IL at 25 °C
(Table ).
Table 4
Viscosity
Values at 25 °C
IL
[P8888][Cl]
[P88814][Cl]
[P88816][Cl]
[P66614][Cl]
viscosity (mm2/s)
284.35
49.79
587.97
2188.66
Conclusions
The
use of phosphonium ILs and that based on ammonium was studied as an
alternative to traditional organic solvents for the separation of
cobalt and nickel. The ILs studied showed selectivity for the cobalt
extraction from nickel. For phosphonium ILs, the equilibrium in the
extraction is reached after 10 min under the experimental conditions
studied. Cobalt extractions near 98% with the trioctyl(alkyl)phosphoniumchloride ILs were obtained. The percentage of cobalt extraction was
practically the same as that obtained with Cyphos IL 101 but much
higher compared to A336, both commercially available. The symmetry
of the cation could affect cobalt extraction, but there is no enough
evidence about it. Additional studies are necessary to establish this
relationship.The Co(II) extraction is strongly dependent on
the initial chloride concentration in the aqueous solution and slightly
dependent on the sulfuric acid concentration. The extraction of cobalt
occurs through an anion exchange mechanism favored by the presence
of hydrogen ions and sulfuric acid, which allow the break of the cobalt
hydration bond. The HCl coextraction is carried out in an acidic medium
and has a negative effect on stripping. The cobalt extraction with
the phosphonium ILs depends slightly on the temperature, resulting
in an endothermic process. For the A336 IL, there is a strong dependence
on the temperature of the system, which may be due to its high viscosity.Cobalt can be extracted from an aqueous solution in sulfate media
adding sodium chloride to the solution. Cobalt extraction with phosphonium
ILs has additional advantages as the process can be carried out with
sodium chloride instead of hydrochloric acid, which translates into
easy handling, lower costs in reagents and equipment, and risk reduction.
The process is facilitated by the cobalt stripping into water without
adding acids, which also reduced the cost.
Authors: Gabriela Adamová; Ramesh L Gardas; Luís Paulo N Rebelo; Allan J Robertson; Kenneth R Seddon Journal: Dalton Trans Date: 2011-10-13 Impact factor: 4.390
Authors: Gabriela Adamová; Ramesh L Gardas; Mark Nieuwenhuyzen; Alberto V Puga; Luís Paulo N Rebelo; Allan J Robertson; Kenneth R Seddon Journal: Dalton Trans Date: 2012-06-07 Impact factor: 4.390
Authors: Ann E Visser; Richard P Swatloski; W Matthew Reichert; Rebecca Mayton; Sean Sheff; Andrzej Wierzbicki; James H Davis; Robin D Rogers Journal: Environ Sci Technol Date: 2002-06-01 Impact factor: 9.028
Authors: Huimin Luo; Sheng Dai; Peter V Bonnesen; A C Buchanan; John D Holbrey; Nicholas J Bridges; Robin D Rogers Journal: Anal Chem Date: 2004-06-01 Impact factor: 6.986