Escolar Documentos
Profissional Documentos
Cultura Documentos
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
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
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
68
Cobalt
Nickel
Log D
M2
aq 2HA2 org
MA2 HA2 org 2Haq ;
2
K ex MA2 HA2 org Haq 2 =M2
aq HA2 org ;
-1
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.
By substituting Eq. (3) into Eq. (2) and converting into logarithmic form the following equations are obtained.
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
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
0.1
0.25
0.5
1.0
5.60
5.53
5.47
5.40
Average
5.50
Average
8.37
69
2.0
3.0
3.5
4.0
4.5
5.5
6.0
5.29
5.43
5.56
5.40
Average
8.40
8.48
8.60
8.60
5.42
8.52
Cobalt
Nickel
80
Average
% Extraction
pH
100
60
40
20
0
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.
70