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Liquid-liquid extraction of Co(II) from nitrate solution using TOA

Archita Mohanty a, Niharbala Devi a,b,⇑, Lala Behari Sukla a, Nandita Swain c
a
Biofuels and Bioprocessing Research Center, Institute of Technical Education and Research, Siksha ‘O’ Anusandhan [Deemed to be University], Bhubaneswar 751030, India
b
Department of Chemistry, Institute of Technical Education and Research, Siksha ‘O’ Anusandhan [Deemed to be University], Bhubaneswar, Odisha, India
c
Department of Chemistry, College of Basic Science and Humanities, Odisha University of Agriculture and Technology, Bhubaneswar, India

a r t i c l e i n f o a b s t r a c t

Article history: Cobalt has widespread industrial applications but if present in excess amounts it may cause several nox-
Received 14 December 2019 ious effects. Liquid-liquid extraction process can be useful in cleaning the environment from harmful
Received in revised form 13 January 2020 chemical pollutants. Solvent extraction of cobalt using cobalt nitrate as the feed solution and triocty-
Accepted 17 January 2020
lamine (TOA) as the extractant in toluene was carried out where the effects of nitric acid concentration,
Available online xxxx
equilibration time, concentration of the extractant and cobalt ions had been investigated. The percentage
extraction of Co(II) decreased upon increasing the concentration of acid. A time of 15 min was needed to
Keywords:
achieve the extraction equilibrium. Highest percentage extraction of cobalt was achieved using 0.1 M
Tri-n-octylamine (TOA)
Liquid-liquid extraction
TOA which is 99%. Cobalt loading increased with increase in metal ion concentration. Presence of nitrate
Cobalt(II) ions had almost no significance in the extraction process. The loaded organic phase was stripped using
Potassium nitrate different stripping agents and 99.15% back extraction was achieved with 0.1 mol/L (NH4)2CO3. The extrac-
Stripping tion mechanism was proposed from the FTIR and slope measurement.
Ó 2020 Elsevier Ltd. All rights reserved.
Selection and Peer-review under responsibility of the scientific committee of the National Conference on
Trends in Minerals & Materials Technology.

1. Introduction extremely harmful because it emits cancer causing gamma rays.

Hazardous wastes must undergo proper treatment before dis-
Cobalt is one of the three naturally occurring magnetic metals charging into environment. Several treatment techniques are avail-
among iron and nickel. Cobalt is generally associated with nickel able such as ion exchange, precipitation, adsorption,
in nature. The major sources of production of nickel and cobalt electrochemical deposition, neutralization, solid-liquid extraction,
are from certain raw materials like oxide and sulfide ores, scrap, liquid-liquid extraction, etc. [4]. Among all these type of chemical
sludges, dust, spent catalysts, etc. [1]. Cobalt-based alloys are wear methods, liquid-liquid extraction is an entrenched procedure for
and corrosion resistant and are used for making turbine blades for extractive separation of metallic ions subsequent to leaching
aircraft jet engines, orthopedic implants and super alloys such as which are employed for electrowinning processes. It allows recy-
stellite which is the largest consumer of cobalt metal. Cobalt is cling of metal ions from both diluted and concentrated solutions
widely used in lithium ion battery, electroplating and as oxidation [5]. This method of extraction and separation is an economical pro-
catalysts [2]. Cobalt is also used in radiotherapy, sterilization, den- cedure for the treatment of scrap metal due to its simple extraction
sity measurements and tank fill height switches. The primary procedure, rapidly developing method and coherent selectivity. A
applications of cobalt are in chemical sector which account for half literature survey for the past 2 decades revealed that majority of
of the total global demand. Moreover, cobalt is a key constituent of the research papers deals with the fundamental features of extrac-
cobalamin (vitamin B12) and plays a vital function in animal meta- tion and applications in the extraction of cobalt and nickel by
bolism. But if present in surplus amounts it can cause several lethal mainly employing phosphorus based extractants from sulfate
effects which may cause genetic and metabolic disorders [3]. media. An extensive variety of extractants branching as acidic,
Cobalt-60 isotope which is produced for commercial purposes is chelating, basic or solvating solvents or their mixtures were
employed and tested to extract cobalt.
⇑ Corresponding author at: Biofuels and Bioprocessing Research Center, Institute The extraction of cobalt and nickel using acidic extractants like
of Technical Education and Research, Siksha ‘O’ Anusandhan [Deemed to be Cyanex 272, Cyanex 301 and Cyanex 302 from sulfate medium was
University], Bhubaneswar 751030, India. reported by Tait [6]. It was found that all these extractants
E-mail address: niharbaladevi@soa.ac.in (N. Devi).

https://doi.org/10.1016/j.matpr.2020.01.381
2214-7853/Ó 2020 Elsevier Ltd. All rights reserved.
Selection and Peer-review under responsibility of the scientific committee of the National Conference on Trends in Minerals & Materials Technology.

Please cite this article as: A. Mohanty, N. Devi, L. B. Sukla et al., Liquid-liquid extraction of Co(II) from nitrate solution using TOA, Materials Today: Pro-
ceedings, https://doi.org/10.1016/j.matpr.2020.01.381
2 A. Mohanty et al. / Materials Today: Proceedings xxx (xxxx) xxx

selectively extracted cobalt and the order of separation is Cyanex and disengagement of both aqueous and organic phases, the
301 > Cyanex 272 > Cyanex 302. Monzyk et al. [7] reported the sol- metal ion concentration was determined by analyzing the aque-
vent extraction of cobalt using hydroxamic acids in which the ous phase at 585 nm using UV–visible spectrophotometer
cobalt bearing aqueous solutions having equilibrium pH atleast 7 (SYSTRONICS 105). The concentration of metal ion in the organic
was contacted with hydrocarbon solvent comprising of N-alkyl phase was calculated by the difference of concentration of metal
alkanohydroxamic acid and extracted cobalt from the aqueous ion in the aqueous phase before and after extraction. After the
solution. Sayar et al. [8] have reported on the extraction of cobalt disengagement of phases, the organic solution was collected, fil-
(II) using Alamine 336 diluted with m-xylene from aqueous tered and stored in an air tight container for spectroscopic stud-
hydrochloric acid solutions. The work predicted that Alamine 336 ies. FTIR spectra of pure extractant and loaded extractant were
is a suitable reagent which extracted more than 90% of cobalt at carried out with Frontier FT-IR Spectrometer, Perkin Elmer. The
5 M HCl. Devi et al. [9] studied on the solvent extraction and sep- distribution ratio was evaluated from the ratio of concentration
aration of Mn(II) and Co(II) from sulfate solutions and found that of Co(II) in organic phase separated from that of aqueous phase
manganese was more preferably extracted over cobalt and after extraction. The percentage of extraction (E) was determined
D2EHPA was found the most appropriate extractant in this separa- from D values as 100D/D + 1.
tion process. Solvent extraction of Co(II) ions was studied by Rafigi
et al. [3]. It showed the extractive properties of 2-Hydroxy-1-
3. Results and discussions
naphthaldoxime and 1-hydroxy-2-naphthaldoxime towards Co(II)
ions from aqueous phase of sodium chloride (NaCl) solution. A syn-
3.1. Variations of equilibration time
ergistic effect was shown by the solvating solvents and basic
extractants like TOPO, TBP, T2EHP, TBA, TOA and DMSO on the
The variation of equilibration time on the extraction of Co(II)
extraction of Co(II) ions as studied from the oximes. Solvent extrac-
using 0.005 mol/L TOA was studied from the feed solution of
tion and recovery of metals like cobalt, nickel and copper from the
0.0005 mol/L Co(NO3)2 and 0.1 mol/L HNO3. The time variation
leach liquor of a sulfide concentrate was studied by Sahu et al. [10].
range was from 1 min to 30 min and the results which are pre-
Copper was first extracted from the leach liquor and from the
sented in Fig. 2 showed that the extraction of Co(II) increased with
copper-free raffinate Co and Ni were recovered using Cyanex
increase in equilibration time up to 15 min and there was no effect
272. Banerjee et al. [11] reported a synergistic behavior of cobalt
with further rise in shaking time on percentage of extraction of
(II) ions using b-hydroxyl napthaldoxime and neutral donors. They
cobalt. The extraction efficiency (% Extraction) increased from
reported that the typical pH ranges from 8 to 9 for the extraction of
10% (1 min) to 70% (15 min). Hence in all the experiments
cobalt using ligand-donor combination. Dreisinger et al. [12]
15 min of equilibration time was fixed.
reported the solvent extraction and separation of cobalt and nickel
using 2-ethylhexlylphosphonic acid mono-2-ethylhexyl ester(PC-
88A). The separation factor varies with the pH and concentration 3.2. Impact of nitric acid concentration
of the extractant and the cobalt loading increased approximately
by 75% and then decreased slightly while approaching saturation. The impact of nitric acid concentration on extractive behavior
In the present research attempt, an investigation has been made of cobalt (0.0005 mol/L) was studied using two different concen-
to extract cobalt(II) using Alamine 300 i.e. tri-n-octyl amine (TOA) tration of TOA i.e. 0.0025 mol/L TOA and 0.005 mol/L TOA. The
from aqueous nitrate solution. The effect of different parameters nitric acid concentrations was varied from 0.005 mol/L to
such as concentration of nitric acid, equilibration time, concentra- 1 mol/L. It was found that the extraction of cobalt decreased
tion of organic phase, aqueous phase concentration, presence of upon increasing the nitric acid concentration for both variants
nitrate ions have been investigated. Stripping process had also of extractant concentrations (Fig. 1). The percentage extraction
been carried out to know the possible metal recovery from the of cobalt(II) using 0.0025 mol/L TOA decreased from 56.7% at
metal loaded organic solution. acid concentration of 0.005 mol/L to 16.7% with nitric acid con-
centration of 1 mol/L. Similarly, the percentage extraction of
cobalt decreased from 80% to 16.7% at nitric acid concentration
2. Experimental of 0.005 mol/L to 1 mol/L. As the extraction percentage using
0.0025 mol/L TOA was found to be very low as compared to
2.1. Solutions and reagents 0.005 mol/L TOA, so the latter concentration of the extractant
was taken into consideration and used in further parameters
The aqueous stock solution of Co(II) of 0.01 mol/L was prepared optimization studies. The nitric acid concentration was also
by weighing the required amount of cobalt nitrate, Co(NO3)2 in taken as 0.1 mol/L because moderate extraction of cobalt (70%)
double distilled water. Sample of trioctylamine (TOA) was supplied was achieved. Hence, other parameters could be varied to find
by Sigma-Aldrich and it was diluted using toluene. The stock solu- the effect.
tion of TOA (0.05 mol/L) was prepared by weighing the desired
amount of extractant. Working solutions of both aqueous
3.3. Effect of TOA concentration
(0.0005 mol/L) and organic (0.005 mol/L and 0.0025 mol/L) were
prepared by diluting both the aqueous and organic stock solutions
Maximum extraction or complete removal of metal from the
as per the requirement. The remaining other reagents of analytical
solution is a major factor which could be evaluated by varying
grade were used.
the TOA concentration. For this, the TOA concentration was var-
ied from 0.0025 mol/L to 0.1 mol/L where the metal ion in the
2.2. Experimental methods solution was maintained at 0.0005 mol/L. It was observed that
the cobalt extraction increased upon rise in concentration of
The experimental route for the extraction of the metal was the extractant and maximum extraction of 99% was reported
performed by equilibrating equal volumes (10 mL) of aqueous with 0.1 mol/L TOA in toluene (Fig. 3). A plot of log D vs. log
phase with organic phase with the help of a separating funnel [TOA] shown in Fig. 4 gave a slope of 1.80 which gave the infor-
for 15 min, excluding for time variation. All the experiments were mation of involvement of two moles of TOA for one mole of Co
being carried out at room temperature. After the equilibration (II) ion.

Please cite this article as: A. Mohanty, N. Devi, L. B. Sukla et al., Liquid-liquid extraction of Co(II) from nitrate solution using TOA, Materials Today: Pro-
ceedings, https://doi.org/10.1016/j.matpr.2020.01.381
 A. Mohanty et al. / Materials Today: Proceedings xxx (xxxx) xxx 3

Fig. 3. Effect of TOA concentration on cobalt extraction from 0.1 mol/L HNO3 and
Fig. 1. Variations of equilibration time upon cobalt extraction using 0.005 mol/L
0.0005 mol/L Co(NO3)2.
TOA in toluene.

Fig. 4. Plot of Log D versus log [TOA].

Fig. 2. Impact of HNO3 concentration on the extraction of Co(II) from 0.0005 mol/L
Co(NO3)2 from 0.0025 mol/L TOA and 0.005 mol/L TOA in toluene.
Co(NO3 )4 2
+ 2R3 Nþ HNO3

(R3 NH)2 Co(NO3 )4 + 2NO3
ð2Þ

3.4. Metal ion concentration variation Where, R = C24H51N

Intake of more amounts of metal ions by the extractant gave a

3.5. Effect of nitrate ions
positive sign to the extractant. To find out the loading ability of
TOA, a set of experiments was carried out where the cobalt concen-
The different concentrations of potassium nitrate varying from
tration was varied from 0.0005 mol/L to 0.01 mol/L with 0.1 mol/L
a range of 0.01 mol/L to 0.2 mol/L were used to analyze the
HNO3 using 0.005 mol/L TOA. Though the percentage of extraction
involvement of nitrate ions during the extraction of cobalt from
of Co(II) decreased from 70% to 20% with increase in cobalt concen-
the solution of 0.0005 mol/L Co(II) and 0.1 mol/L HNO3 using
tration in the aqueous solution but the concentration of cobalt in
0.005 mol/L TOA in toluene. From the figure it stated that the
the loaded organic phase increased from 21 mg/L to 118 mg/L
extraction of the cobalt ion was not affected by the presence of
(Fig. 5) with increase in cobalt concentration.
nitrate ions (Fig. 7). This is may be due to salting in effect.
In order to examine the mechanism of extraction, FTIR spectra
of trioctylamine (TOA) before and after extraction were recorded.
The spectra of the pure extractant and loaded extractant is
recorded and demonstrated in the Fig. 6. From the spectrum, it
was detected that a peak appearing at 1452 cm
1 in case of pure
TOA shifted to 1424 cm
1 for pregnant TOA indicating N-CH2 sym-
metric stretching vibration. The peak at 1424 cm
1 gave a more
intensified and broader peak after loading. Similarly, a peak corre-
sponding to CH3 bending vibration of bare TOA shifted from
1390 cm
1 to 1370 cm
1 loaded TOA. A characteristic peak was
shown at 1236 cm
1 resulting in C–N stretching vibration. Another
new peak of pure TOA at 1034 cm
1 shifted to 1092 cm
1 with
loaded TOA due to C–N stretching vibrations.
Based on the experimental results, a plausible extraction mech-
anism [13,15] has been proposed which is as below:
R3 N + Hþ NO3

R3 Nþ HNO3

Fig. 5. Amount of cobalt present in organic solution versus amount of cobalt
ð1Þ
present in aqueous solution using 0.005 mol/L TOA in toluene.

Please cite this article as: A. Mohanty, N. Devi, L. B. Sukla et al., Liquid-liquid extraction of Co(II) from nitrate solution using TOA, Materials Today: Pro-
ceedings, https://doi.org/10.1016/j.matpr.2020.01.381
4 A. Mohanty et al. / Materials Today: Proceedings xxx (xxxx) xxx

with (NH4)2CO3. It was observed 0.1 mol/L (NH4)2CO3 is a good

stripping agent to recover Co(II) from loaded organic phase of
0.1 mol/L TOA.

3.7. Comparative study

A comparative study on the extraction of Co(II) with TOA and

TOA along with other extractants were presented with the present
investigation in Table 1.

4. Conclusions

Solvent extraction and the distribution ratio for the extrac-

tion of 0.0005 mol/L Co(II) from nitrate medium using TOA in
toluene has been investigated. The equilibration time was
achieved in 15 min. The percentage of extraction decreased
with rise in nitric acid concentration and acid variation was
found highest (80%) using 0.005 mol/L TOA. The extractive per-
centage of cobalt increased asymptotically and reaches a max-
imum of 99.9% at 0.1 mol/L TOA. The cobalt loaded in the
Fig. 6. FTIR spectra of pure TOA in cyclohexane and cobalt loaded TOA in organic phase increased with increase in aqueous phase con-
cyclohexane. centration. The presence of the salt, KNO3 does not reveal effi-
cient extraction performance. The stripping of Co(II) from
loaded organic phase was found to be 99.15% with stripping
agent 0.1 mol/L (NH4)2CO3. The proposed extracted species
was found to be (R3NH)2Co(NO3)4.

CRediT authorship contribution statement

Archita Mohanty: Investigation, Formal analysis, Writing -

original draft. Niharbala Devi: Conceptualization, Supervision.
Lala Behari Sukla: Writing - review & editing. Nandita Swain:
Supervision, Resources.

Declaration of Competing Interest

The authors declare that they have no known competing finan-

cial interests or personal relationships that could have appeared
to influence the work reported in this paper.

Acknowledgement

Fig. 7. Effect of potassium nitrate on cobalt extraction using 0.005 mol/L TOA in
The authors are thankful to S ‘O’ A (deemed to be university)
toluene.
and Odisha University of Agriculture and Technology for their
indebtful help to carry out the experiments.
3.6. Stripping of cobalt
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Table 1
Research on solvent extraction of cobalt with trioctylamine (TOA).

Metal (s) Extractant + diluent Observation References

Co(II) TOA, toluene 99.9% E with 5% v/v TOA, 90% stripping with 5.0 M NH3 solution [14]
Co(II) Alamine 336, m-xylene % E approaches 100% at higher acid concentrations (10 M) [5]
Co(II), Mn(II), Cu(II) TOA and Aliquat 336, benzene ESR studies report that the MCl4 2- moiety in all complexes [15]
had tetrahedral geometry
Co(II) , Ni(II) Alamine 336 % E exceeds 90% at 5 M HCl and approaches 100% at 10 M HCl [16]
Co(II) Acidic- Cyanex 301, D2EHPA, Cyanex 272 %E(acidic)-Cyanex301 > D2EHPA > Cyanex 272 [17]
Basic- TOA, Alamine 336 %E(basic)- TOA > Alamine 336
Co(II) TOA, toluene 99% extraction, 99.15% stripping with 0.1 mol/L (NH4)2CO3 Present study

Please cite this article as: A. Mohanty, N. Devi, L. B. Sukla et al., Liquid-liquid extraction of Co(II) from nitrate solution using TOA, Materials Today: Pro-
ceedings, https://doi.org/10.1016/j.matpr.2020.01.381
 A. Mohanty et al. / Materials Today: Proceedings xxx (xxxx) xxx 5

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Please cite this article as: A. Mohanty, N. Devi, L. B. Sukla et al., Liquid-liquid extraction of Co(II) from nitrate solution using TOA, Materials Today: Pro-
ceedings, https://doi.org/10.1016/j.matpr.2020.01.381