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Separation and Purication Technology 89 (2012) 6670

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Separation and Purication Technology


journal homepage: www.elsevier.com/locate/seppur

Evaluation of n-octyl(phenyl)phosphinic acid (OPPA) as an extractant


for separation of cobalt(II) and nickel(II) from sulphate solutions
S. Mondal a, Vikas Kumar a, J.N. Sharma a,, R.C. Hubli a, A.K. Suri b
a
b

Hydrometallurgy Section, Bhabha Atomic Research Centre, Trombay, Mumbai, India


Materials Group, Bhabha Atomic Research Centre, Trombay, Mumbai, India

a r t i c l e

i n f o

Article history:
Received 8 November 2011
Received in revised form 29 December 2011
Accepted 8 January 2012
Available online 14 January 2012
Keywords:
Solvent extraction
Cobalt(II)
Nickel(II)
Octyl(phenyl)phosphinic acid

a b s t r a c t
Solvent extraction separation of divalent cobalt and nickel from sulphate solutions was studied using
OPPA dissolved in n-dodecane and the optimum conditions for separation of cobalt and nickel were
determined. It was found that extraction of both the metal ions increases with increase in equilibrium
pH. Cobalt was preferentially extracted over nickel in all pH range, DpH0.5 value of 1.8 indicates the possible separation of both the metal ions from each other. Almost complete extraction of cobalt is observed
at pH 4.5 where separation factor (b = DCo/DNi) is approximately 1400, above this pH co-extraction of
nickel increases and reduction in separation factor was observed. The composition of extracted species
determined by slope analysis of the plots of log D vs. log [OPPA]2 and log D vs. equilibrium pH indicates
formation of the species MA2 (HA)2 for both the metal ions. Temperature dependence studies of the
extraction constant Kex, showed that the extraction is enthalpy driven with unfavorable entropy.
OPPA/dodecane was employed for cobalt/nickel separation from rafnate solution obtained during solvent extraction process of spent ammonia cracker catalyst leach solution. 1.0 M OPPA/dodecane in counter-current extraction at O/A of 1.0 was efciently used to separate cobalt from nickel.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Extraction of cobalt and nickel and their separation have been
extensively studied and reviewed from various aqueous streams,
however, owing to their similar chemical properties in aqueous
solutions, development of separation routes to obtain pure cobalt
and nickel compounds from different primary and secondary
resources is difcult using classical methods of separations such
as precipitation, oxidation and crystallization. Solvent extraction
using solvents selective for one of the metal ions has been successfully employed for this purpose [1,2]. Literatures on this separation
indicate extensive use of organo-phosphorus based extractants of
the class phosphoric, phosphonic and phosphinic acids [37]. Some
of the reports also use tributyl phosphate, thiophosphinic acid, LIX
860 (5-dodecylsalicylaldoxime) and trioctyl amine for this separation [8,9]. In sulphate solutions cobalt and nickel exist as divalent
hydrated ions and extraction takes place through cation exchange,
therefore, organo-phosphorus acids as cation exchangers are
employed for their extraction and separation. Much of the beginning work has been reported using di(2-ethylhexyl) phosphoric
Corresponding author. Address: Hydrometallurgy Section, MPD, MG, Bhabha
Atomic Research Centre, Trombay, Mumbai 400085, India. Tel./fax: +91 022
25592959.
E-mail address: jnsharma@barc.gov.in (J.N. Sharma).
1383-5866/$ - see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2012.01.015

acid (D2EHPA). Ritcey et al. [10] have reported the rst process
to separate cobalt from nickel by using D2EHPA. In China, several
laboratories and pilot plants have extensively studied separation
of cobalt and nickel using D2EHPA in the early seventies. The
composition of extracted complex with D2EHPA was determined
by Grimm and Kolarik [11,12] as Co(HA2)2 and Ni(HA2)2. Organophosphonates, mainly 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester supplied by Daihachi Chemical Industry Limited with
the trade name of PC 88-A has shown a Co/Ni separation factor of
about 200 times greater than that of D2EHPA under similar condition of extraction. In 1978, Nippon Mining Corporation started the
use of PC 88-A to extract cobalt in their Hitachi Renery [13]. Similar reagent of the trade name P507 (2-ethylhexyl 2-ethylhexyl
phosphonate) has been used in China for separation of cobalt from
a hydroxide precipitate produced in the nickel anolyte purication
process [14]. A process for separation of cobalt and nickel from a
solution containing 30 g/L each of cobalt and nickel at pH 5.5 by
using 20 vol.% PC88A in kerosene has been patented by Fujimoto
et al. [15]. Di(2,4,4-trimethylpentyl) phosphinic acid, a product of
Cytec chemicals with trade name Cyanex 272 has a much stronger
ability for separation of cobalt from nickel in sulphate solution
than PC 88-A. Rickelton et al. [16] have shown higher separation
factor between cobalt and nickel for Cyanex 272 compared to the
analogous phosphoric and phosphonic acid and obtained pure
cobalt metal from a mini-plant scale continuous counter-current

S. Mondal et al. / Separation and Purication Technology 89 (2012) 6670

extraction using Cyanex 272. Outokumphu Harjavalta Metals have


used Cyanex 272 to recover cobalt from nickel matte leaching solution containing about 1.0 g/L of cobalt and 130 g/L of nickel. It employs four stages of extraction, ve stages of scrubbing and four
stages of stripping with the vertical smooth ow mixer-settlers,
to obtain strip solution containing 110 g/L cobalt and 0.02 g/L nickel [17]. Devi et al. [6] have indicated that a high separation factor of
about 3000 is obtained between cobalt and nickel at pH 7.2 by
using Cyanex 272. Danesi et al. [18] have also used the same
extractant for cobaltnickel separation and showed that the separation factor is enhanced by decreasing the unbound concentration
of Cyanex 272 in the organic phase.
Extraction processes for cobalt and nickel separation with
Cyanex 272 are effectively used in the pH range of 6.27.3. This
pH is difcult to adjust and maintain as it is very close to hydrolysis pH of cobalt and nickel. Therefore, there is a need for an alternate extractant which can work at lower pH, so as to eliminate the
need for stringent pH control as required in the case of Cyanex 272.
In the present work, the extraction and separation of cobalt and
nickel from sulphate solution is carried out using octyl(phenyl)phosphinic acid (OPPA). OPPA is more acidic than its dialkyl counterpart as phenyl group has stronger drawing ability for electrons
than alkyl groups, resulting in the OH group more acidic in the
case of phenyl substituted phosphinic acid. The pKa of OPPA is reported to be 4.63 which is less than pKa of dialkyl phosphinic acids
(Cyanex 272 and di-n-octylphosphinic acid) by approximately
0.8 units [19]. The more acidic OPPA can therefore, be used for separation from more acidic aqueous solutions, thus, solving many
problems associated with operation of extraction process of cobalt
and nickel at pH range of 6.27.3, required for effective separation
using Cyanex 272. In the present studies, OPPA has been tested for
extraction and separation of cobalt and nickel from synthetic solutions as well as from the rafnate solution of spent ammonia
cracker catalyst process having pH in the range of 4.44.7.

2. Experimental
2.1. Reagents
OPPA was synthesized according to the procedure reported
elsewhere [19]. The product obtained on reuxing ethanolic solution of phenyl phosphinic acid, 1-octene and benzoyl peroxide
for 24 h. was extracted in toluene and washed with 1.0 M HCl
and successively with water to remove any unreacted phenyl phosphinic acid. The product was then concentrated by degassing at
75 C and 0.01 mm Hg pressure. Potentiometric titration of the
product in 75:25 volume ratios of ethanol to water showed a purity
of more than 99% with no dibasic acid and less than 1.0% of neutrals impurities. The structural formula of OPPA is shown in Fig. 1.
Phenyl phosphinic acid was synthesized from FriedelCrafts
reaction of benzene, phosphorus trichloride and anhydrous aluminum trichloride [20]. n-Dodecane was used as diluent and obtained
from M/s. Numex Chemical Corporation, India. Demineralised
water was used for preparation of all the aqueous solutions. The
stock solutions of cobalt(II) and nickel(II) sulphate each of 0.17 M
metal ions were prepared by dissolving analytical grade chemicals

C 8 H17

O
P
OH

Fig. 1. Structural formula of octyl(phenyl)phosphinic acid.

67

in demineralised water. 0.6 M sodium sulphate as inert noncomplexing electrolyte was also added to the stock solution, with
the assumption to keep ionic strength of the medium constant
during extraction. The sulphate solution mentioned in this paper
is contra-anion of cobalt, nickel and sodium ions, the concentration
of which in the stock solution is approximately 0.94 M. pH adjustment of the solutions was done by adding concentrated solutions
of NaOH and H2SO4.
2.2. Extraction procedure
Extraction experiments were carried out by the conventional
batch method using separating funnels. Organic solutions were
prepared by dissolving appropriate amount of extractant in
n-dodecane. The initial pH of the aqueous solutions was adjusted
to desired value before the equilibration was carried out. pH measurements were done by a combination glass electrodes calibrated
with buffer solutions and the possible error in measurements was
less than 0.2 pH unit. Aqueous solutions (10 ml) containing
0.017 M Co2+ and 0.017 M Ni2+ ions separately, were equilibrated
with equal volume of 1.0 M OPPA in n-dodecane for 15 min. After
phase separation, equilibrium pH of the rafnate solutions was
measured. The solutions were diluted as required with dilute HCl
(1 M) and analysis of metal values was carried out with GBC
make Model Avante 1.31 atomic absorption spectrometer. The
metal values in the organic solutions were calculated by material
balance. The error in the analysis was within 2.0% and the detection limit for cobalt and nickel was 0.5 lg/mL. The distribution
ratio (D) for the metal ions is calculated as the ratio of concentration of metal ion in the organic phase to the aqueous phase. The
stripping studies were carried out with dilute sulphuric acid
solutions prepared from a standard 1.5 M sulphuric acid solution.
For measuring the effect of temperature on distribution ratio,
experiments were conducted in a thermostat (0.5 C) with
mechanical shaking for 30 min. Temperature was varied in the
range of 300333 K. Agitated samples were then left in the thermostat for half an hour to allow complete separation of two
phases. The aqueous phases were separated and analyzed for metal
ions.
The extraction data generated from synthetic solutions were
used for separation of both the metals from each other present in
the rafnate solution of spent ammonia cracker catalyst process
obtained from solvent extraction of spent ammonia cracker catalyst leach liquor.
3. Results and discussion
3.1. Effect of equilibrium pH
The extraction of cobalt and nickel from sulphate solution was
studied using sodium salt of 1.0 M OPPA in the initial pH range
of 1.06.5, corresponding to the change in the equilibrium pH from
1.0 to 7.0, respectively. The plots of log D vs. equilibrium pH (Fig. 2)
showed the increase in extraction of both the metal ions with increase in equilibrium pH. The pH0.5 (at log D = 0) values of cobalt
and nickel are 3.0 and 4.8, respectively, which indicate that cobalt
is extracted at lower pH value than nickel. These pH values for
extraction by OPPA are lower than the corresponding dialkyl phosphinic acid, Cyanex 272, by a pH unit of approximately 22.5 [7], as
OPPA being more acidic than Cyanex 272 it can, therefore, be used
in extraction processes at lower aqueous pH. The DpH0.5 value of
cobalt and nickel extraction in the present experimental conditions
is obtained as 1.8. The extraction of both the metal ions increases
with increase in equilibrium pH, almost complete extraction of
cobalt was obtained between pH 4.2 and 4.5 where separation

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S. Mondal et al. / Separation and Purication Technology 89 (2012) 6670

therefore largely associated with two dimers or four formula units


of OPPA in organic phase. Extraction of cobalt and nickel from sulphate medium under these conditions thus can be represented as:

Cobalt
Nickel

Log D

M2
aq 2HA2 org
MA2 HA2 org 2Haq ;

where (HA)2 represents dimer molecule of OPPA.


The conditional extraction equilibrium concentration constant,
Kex, in reaction (1) is described as:

2
K ex MA2 HA2 org Haq 2 =M2
aq HA2 org  ;

-1

D is distribution coefcient and dened as:


-2

D MA2 HA2 org =M2


aq 
2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

Equilibrium pH
Fig. 2. The dependence of D on equilibrium pH. Organic phase: 1.0 M OPPA,
aqueous phase: cobalt sulphate (0.017 M Co) and nickel sulphate (0.017 M Ni)
solution, O/A = 1. T = 303 K.

factor (b = DCo/DNi) obtained is approximately 1400, above this pH


co-extraction of nickel was also higher and separation factor reduces. The plots of Fig. 2 were linear with slope of 1.94 for cobalt
and 1.91 for nickel indicating the exchange of approximately two
moles of H+ with one mole of extracted metal species.
3.2. Effect of extractant concentration
The effect of OPPA concentration on the extraction of cobalt and
nickel each at 0.017 M was studied in the range of 0.11.0 M OPPA/
n-dodecane solution at initial aqueous pH of 4.5. Mason et al. [19]
have reported that OPPA exists as dimer in non-polar organic diluents, at low metal ion concentration and assuming the OPPA
monomer concentration as negligible, the analytical concentration
of OPPA can be expressed as [OPPA] = 2 [(OPPA)]2. The log D vs. log
[OPPA]2 plots for both the metal ions are shown in Fig. 3. The plots
were straight lines with slopes of 2.2 and 1.66 for cobalt and nickel,
respectively, indicating the association of two moles of extractant
in the extracted metal species. Log D vs. log [OPPA]2 plots for both
the metal ions were also drawn at different metal ion concentrations (0.008 and 0.034 M), the plots were straight lines and no
change in the slopes was observed. This ascertains that the stoichiometry of metalOPPA complexes does not change under the studied experimental conditions. As OPPA exists as dimer in non-polar
organic diluents, the doubly charged cobalt and nickel ions are

By substituting Eq. (3) into Eq. (2) and converting into logarithmic form the following equations are obtained.

K ex DHaq 2 =HA2 org 2


log K ex log D 2 log

Haq 

4
 2 log HA2 org 

The log Kex values for cobalt and nickel were calculated at pH
4.5 and at different concentrations of OPPA, also at constant
extractant concentration and at different pH. The log Kex values
are summarized in Tables 1 and 2. The values obtained are nearly
constant with an average value of 5.50 for cobalt and 8.48 for
nickel. Log Kex values calculated at constant extractant concentration and at different pH, are also constant with the average values
of 5.42 for cobalt and 8.52 for nickel. This indicates that the proposed extraction equilibrium, as dened by Eq. (5), is valid under
the investigated extraction conditions.
3.3. Loading capacity determination
Loading capacity of OPPA was determined by contacting various
concentrations of OPPA/n-dodecane repeatedly with aqueous solutions containing 0.17 M cobalt at initial pH of 4.5. The phases were
separated after equilibration and cobalt content in the aqueous
phase was determined. The amount of cobalt transferred into the
organic phase in each contact was calculated by mass balance
and the cumulative concentration in the organic phase after each
contact was determined. Loading capacity of 1.0 M and 0.5 M
OPPA/n-dodecane solution was found to be 0.315 and 0.166 M,
respectively. The loading capacity of cobalt in the organic phase
corresponds to approximately 1:3 stoichiometry between cobalt
to OPPA, thus at higher metal loadings, decrease in the content of
extractant associated with the metal ion was observed.
3.4. Effect of temperature on extraction

Nickel
Cobalt

The effect of temperature on the extraction of cobalt and nickel


was studied in the temperature range of 303333 K from the aqueous solutions of cobalt and nickel (0.017 M each) at initial aqueous
pH of 4.5 using 1.0 M OPPA/n-dodecane solution. It was observed
that extraction of both the metal ions is exothermic in nature as
extraction decreases with increase in temperature. This decrease
in extraction with increase in temperature may be due to decrease

log D

Slope = 2.2

Slope = 1.66

-1

Table 1
Extraction constant (log Kex) of cobalt and nickel at different concentrations of OPPA,
T = 303 K, pH = 4.5.

-2
-1.2

-1.0

-0.8

-0.6

-0.4

-0.2

log [OPPA] 2
Fig. 3. The dependence of D on initial concentration of (OPPA)2. Organic phase:
OPPA in dodecane, aqueous phase: cobalt sulphate (0.017 M Co) and nickel sulphate
(0.017 M Ni) solutions at initial pH of 4.5, O/A = 1. T = 303 K.

[OPPA] M

log Kex (Co)

0.1
0.25
0.5
1.0

5.60
5.53
5.47
5.40

Average

5.50

log Kex (Ni)


8.16
8.36
8.50
8.48

Average

8.37

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S. Mondal et al. / Separation and Purication Technology 89 (2012) 6670


Table 2
Extraction constant (log Kex) of cobalt and nickel at different pH, [OPPA] = 1.0 M,
T = 303 K.
log Kex (Co)

2.0
3.0
3.5
4.0
4.5
5.5
6.0

5.29
5.43

5.56
5.40

Average

log Kex (Ni)

8.40

8.48
8.60
8.60

5.42

8.52

Cobalt
Nickel

80

Average

% Extraction

pH

100

60
40
20
0

in stability of the extracted complex with increase in temperature.


These results are contrary to the endothermic nature of extraction
obtained in the case of Cyanex 272 based solvents [9,21], where
the extraction is carried out at elevated temperature for improved
separation of cobalt and nickel. The results of temperature effect
on extraction are shown in Fig. 4 as a function of log Kex vs.
1000/T, K1 for cobalt and nickel. Enthalpy and entropy of extraction were calculated from slopes (DH0/2.303 R) and intercepts
(DS0/2.303 R) of the Vant Hoff equation (Eq. (6)).
0

log K ex DH =2:303 RT DS =R

Log Kex

-6.5
-7.0
-7.5
-8.0
-8.5
-9.0
-9.5
3.00

3.05

3.10

3.15

3.20

3.25

3.30

1000/T, K -1
Fig. 4. Effect of temperature on the equilibrium constant of cobalt and nickel.
Organic phase: 1.0 M OPPA, aqueous phase: cobalt sulphate (0.017 M Co) and nickel
sulphate (0.017 M Ni) solutions at initial pH of 4.5, O/A = 1.

[Co]org , g/L

14

-6.0

18

The plots of log Kex vs. 1000/T for cobalt and nickel are straight
lines, the slopes and intercepts for cobalt and nickel are 4443, 3260
and 20.055, 19.277, respectively. The values of enthalpy and
entropy of extraction for cobalt and nickel are 85.89 kJ mol1,
63.63 kJ mol1 and 387.0 J mol1K1, 374.5 J mol1K1,
respectively.
Most of the liquid cation exchange extraction processes are exothermic and driven by large and negative enthalpy and opposed by
the negative entropy. The extraction of cobalt and nickel by OPPA
results in a negative enthalpy (DH < 0) and entropy change
(DS < 0). The negative enthalpy change is due to the coordination
of cobalt and nickel by organic ligand OPPA which replaces the relatively weak hydrogen bonds with stronger metalligand coordination bonds and negative entropy change is due to the increase
of order caused by the formation of new bonds and also to hydration of the exchanged proton over the disorder generated by metal
ion dehydration. The enthalpy change of cobalt extraction is more
negative than that of nickel, thus, indicating a more favorable
extraction of cobalt over nickel.

Cobalt
Nickel

Fig. 5. Effect of equilibrium pH on the extraction of cobalt and nickel from the
rafnate solution containing 17 g/L Co and 0.5 g/L Ni as sulphate at pH of 4.6.
Organic: 1.0 M OPPA, O/A = 1. T = 303 K.

16

-5.5

Equilibrium pH

-5.0

12
10
8
6
4
0

10

12

14

16

18

[Co]aq, g/L
Fig. 6. McCabeThiele plot for extraction of cobalt from rafnate solution of spent
ammonia cracker catalyst solvent extraction process. Organic: 1.0 M OPPA, aqueous
phase: rafnate solution containing 17 g/L Co and 0.5 g/L Ni as sulphate at pH of 4.6.
T = 303 K.

3.5. Separation of cobalt and nickel from spent ammonia cracker


catalyst
Spent ammonia cracker catalyst generated by heavy water
plants has been an important secondary source for cobalt production. Different methods have been used for recovery of cobalt from
this spent catalyst [22,23]. The catalyst containing about 22% wt/
wt cobalt and 0.21% wt/wt nickel on Al2O3/Fe2O3 support was leached with sulphuric acid in oxidizing medium for complete dissolution of all the metal ions. Iron and aluminum were extracted by
85% saponied 0.5 M HDEHP/0.7 M TBP-dodecane solvent leaving
cobalt and nickel in the rafnate. The rafnate containing 17 g/L
Co and 0.5 g/L Ni as sulphate solution at pH of 4.6 was taken for
Co/Ni separation and referred as feed for further separation studies. 1.0 M OPPA/dodecane was used for cobalt/nickel separation
from feed solution. The initial pH of feed solution was varied and
the percentage extraction of cobalt and nickel was determined.
The plot of % E vs. equilibrium pH (Fig. 5) shows the increase in
percentage extraction of both the metal ions with increase in equilibrium pH. However, the % E of nickel in this case was much less
compared to extraction of nickel as shown in Fig. 2, where nickel
was taken alone in the solution. This reduction in nickel extraction
from the solution containing higher concentration of cobalt compared to nickel is because of crowding effect produced due to high

70

S. Mondal et al. / Separation and Purication Technology 89 (2012) 6670

extraction of cobalt. From the graph it can be seen that almost


complete extraction of cobalt with co-extraction of about 25% nickel was observed at pH 4.5. To evaluate the number of stages required for the extraction of cobalt from the feed solution at a
chosen O/A ratio, the McCabeThiele plot (Fig. 6) was constructed
at O/A ratio varying from 1:7 to 5:1. The results of the plot suggested that a three-stage extraction at equal phase ratio will be
sufcient to load maximum cobalt from the feed solution. A
three-stage counter-current extraction study at equal phase ratio
(50 ml each) was carried out in separating funnel. Analysis of cobalt and nickel concentrations in aqueous phase indicates complete extraction of cobalt with co-extraction of nickel of about
0.1 g/L. The co-extracted nickel was scrubbed in a single contact
using 2.0 g/L cobalt sulphate solution at pH of 4.8 at O/A ratio of
1:2. Complete stripping was obtained with 1.0 M H2SO4. The product solution of cobalt sulphate was analyzed and found to contain
less than 1.0 mg/L nickel.
4. Conclusions
Solvent extraction of cobalt and nickel from sulphate solution
has been carried out using OPPA diluted with n-dodecane. Percentage extraction of both the metal ions increases with increase in
extractant concentration. The extraction data have shown that cobalt is completely extracted and effectively separated from nickel
with high separation factor of about 1400 at pH of 4.5.
As OPPA is more acidic than Cyanex 272, it therefore can be
used for separation of cobalt from nickel from more acidic aqueous
solutions, thus, in our present studies we have seen that OPPA
effectively separates cobalt from nickel at a lower pH than Cyanex
272. Use of OPPA at lower pH solves many problems associated
with hydrolysis of cobalt and nickel when Cyanex 272 is employed
for their separation at higher pH of 6.27.3. However, availability
of Cyanex 272 at commercial scale makes the separation process
economically viable, which is yet to be established for OPPA/ndodecane solvent.
The composition of extracted species determined by slope analysis of the plot of log D vs. log [OPPA] at initial pH of 4.5 indicates
the association of two moles of extractant for both the metal ions.
Thermodynamic data on extraction have shown that extraction of
cobalt is more exothermic compared to nickel. The extraction data
have been used for cobalt and nickel separation from rafnate
solution of solvent extraction process of spent ammonia cracker
catalyst leach solution, containing 17 g/L Co and 0.5 g/L Ni as sulphate at pH of 4.6. Optimum conditions for separation were determined and observed that 1.0 M OPPA/dodecane in counter-current
extraction could load complete cobalt along with co-extraction of
about 25% of nickel without adjusting the pH of the feed at O/A ratio of 1.0. Co-extracted nickel was scrubbed using 2.0 g/L CoSO4
solution at pH of 4.8 and O/A ratio of 1:2. Complete stripping
was observed with 1.0 M H2SO4. The analysis of product solution
showed less than 1.0 mg/L of nickel. The promising results obtained in the present studies indicate the possibilities of using
OPPA/n-dodecane solvent for Co and Ni separation from sulphate

solution. Parallel efforts are also being made to produce OPPA at


larger quantities to study continuous counter-current mixer-settler extraction process at pilot scale.
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