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Abstract
Copper was extracted from ammoniacal-ammonium sulfate solutions using emulsion liquid membranes (ELMs) with ketoxime
LIX 84 I as carrier. The extraction process was very fast and almost quantitative extraction was observed in most cases in just two
minutes contact between the feed and the emulsion phases. The optimal pH for extraction was found to be pH 8.1, which limited
the free ammonia transport through the membrane. Loading capacity of the membrane governed the extraction rates. High carrier
concentration and treat ratio led to faster recoveries. Even when copper concentration in feed solutions was N 3000 mg/L, extraction
with ELMs containing 10% (v/v) LIX 84 I in the oil phase and a treat ratio of 1:6 resulted in almost 88% copper recovery in just
three minutes of contact.
2007 Elsevier B.V. All rights reserved.
Keywords: Emulsion liquid membrane; Copper; LIX 84 I; Extraction; Ammonia; Ammonium sulfate
concentration to initial copper concentration (Ce/Ceo) dispersion of the emulsion that increased extraction rates but
versus time. Emulsion globule sizes were measured by caused significant emulsion breakage. It was also found that
photographic technique discussed by Sengupta et al., emulsions formulated with 3 wt.% surfactant concentration in
(2006a). The emulsions were characterized by measure- the membrane phase were adequate for membrane stability.
Increasing surfactant concentration to 5 wt.% did not have any
ment of viscosity, internal drop size distribution and
significant effect on the extraction rates, nor did it enhance the
interfacial tension between the emulsion and feed phase
membrane stability; but reducing the surfactant concentration
using methods discussed in our earlier paper (Sengupta to 2 wt.% caused the emulsion to disintegrate very rapidly when
et al., 2006b). dispersed in the feed. All investigations were subsequently
Equilibration studies were carried out with equal performed using emulsions formulated with 3% Span 80 in the
volumes of feed phase (1000 mg/L Cu) and organic membrane phase and the emulsions were dispersed in the feed
phase containing LIX 84 I (2% to 10% v/v) at 30 C by at 160 rpm.
stirring. Although loading was found to be instanta-
neous, the phases were contacted for 30 min. After phase 4.1. Effect of pH
disengagement and separation, copper concentration in
the aqueous phase was determined. Copper was stripped The effect of feed phase pH on extraction was studied at pH
8.1 and pH 9.1. Emulsions used were formulated with equal
from the loaded organic phase using H2SO4 (1.5 M) as
volume of kerosene and stripping phases giving the internal
the strippant; equal volumes of both phases were taken phase volume fraction = 0.5, carrier concentration Cc = 10%
and vigorously stirred. Copper concentration in the acid (v/v) LIX 84 I, and the internal phase sulfuric acid concentration
phase was determined at definite time intervals to obtain Cio = 1.5 M. The initial feed concentration was Ceo 500 mg/L
the stripping kinetics. and the treat ratio (TR) of the emulsion to the feed was
maintained at 1:6.
4. Results and discussion Fig. 1 shows that the rate of extraction of copper from
ammoniacal-ammonium sulfate solutions is very rapid.
It is well known that leach liquors arising from ammoniacal Quantitative extraction of copper was observed at both pH
leaching contain metals as their ammine complex M (NH3)2+ 4 . values but the rate of extraction at pH 8.1 was considerably
Extraction of copper from ammoniacal solutions using LIX 84 I faster than at pH 9.1. For further investigations the feed phase
can be described by the following chemical reaction: pH was fixed at pH 8.1, which ensured that free ammonia
2 transport across the membrane was minimal. It was observed
CuNH3 4 Aq
2RHorg ACuR2org 2NH
4Aq 2NH3Aq 1 that in just 2 min duration quantitative extraction of copper
occurred at pH 8.1; hence, extraction runs were carried out for
Eq. (1) shows that after extraction there is an increase in the 3 min in most cases. In this short duration of extraction runs
ammonia concentration in the aqueous phase due to release of there was no evidence of membrane breakage or rupture.
ammonia bonded to metal ions leading to an increase in pH.
Nathsarma and Bhaskara Sarma (1993) have reported that in 4.2. Effect of carrier concentration
actual practice often there is no increase in pH due to buffering by
ammonium ion, rather a small decrease due to take up of Carrier concentration in the membrane phase has consid-
ammonia by the solvent. They also observed that copper erable influence on the overall extraction rates in ELMs.
extraction remains steady up to pH 8, but beyond this, copper Sengupta et al. (2006b) observed an increase in copper
extraction decreases slowly up to pH 10.5 and sharply at pH 10.9.
Lee and Chan (1990) extracted ammonia from dilute
solutions into ELM's and they reported the effect of pH on
molecular ammoniaammonium ion shift. Since NH+4 ion is not
soluble in the oil membrane, only free ammonia can be
transported and trapped within the membrane and this requires
the pH to be adjusted 12. These investigators observed that at
pH 9.5, free ammonia content is only 50%; while at pH 8 it is
less than 10%. In view of these findings the effect of pH was
first investigated to establish optimal operating conditions for
copper removal from ammoniacal-ammonium sulfate
solutions.
Pilot experiments revealed that W/O emulsions could be
adequately dispersed in the feed by stirring at 160 rpm. Lower
stirring rates failed to disperse the emulsion adequately leaving
a film of emulsion on the surface of the feed phase. On the other Fig. 1. Effect of feed pH on rate of copper extraction. ( = 0.5,
hand, higher stirring rates of 190 rpm gave a very fine Wsurf = 3 wt.%, Cio = 1.5 M, Cc= 10% v/v, Ceo 500 mg/L, TR= 1: 6).
314 B. Sengupta et al. / Hydrometallurgy 89 (2007) 311318
tension observed between the emulsion and feed phase for the
emulsions containing 10% LIX 84 I in comparison with
emulsions containing 5% LIX 84 I.
Lower interfacial tension results in formation of smaller
globules under otherwise identical conditions as reported
earlier in Section 4.2. Hence, for the same treat ratio it results in
more globules formed, thereby generating larger contact area at
the feedmembrane interface causing an increase in the rates of
mass transfer. More importantly smaller sized globules also
result in shorter diffusion path lengths that the oximecopper
complex has to travel within the globule to get stripped. Hence,
if emulsion globules are smaller in size extraction will be more
rapid as observed in case I.
Fig. 6. Effect of initial copper concentration (Ceo) on rate of copper
extraction using 5% LIX 84 I. ( = 0.5, Wsurf = 3 wt.%, Cio = 1.5 M, 4.5. Effect of treat ratio
Cc = 5% v/v, pH = 8.1, TR = 1: 6).
Treat ratio is a measure of emulsion holdup in the system.
An increase in treat ratio leads to an increase in emulsion
Fig. 7 shows the effect of Ceo for emulsion containing 10% holdup. It results in an increase in the overall extraction
LIX 84 I in the membrane phase. Ceo was varied in the range of capacity of the emulsion due to increase in the amount of
497 mg/L to 3120 mg/L. The extraction curves for 497 mg/L membrane phase and the stripping phase as well as the amount
and 1064 mg/L converge together after 60 s duration while the of carrier. An increase in treat ratio also results in an increase of
extraction curves for 1925 mg/L and 3120 mg/L diverge out. the overall surface area of the system, it is therefore expected
Since the copper loading capacities in the emulsions containing that increase in treat ratio would also result in increase in the
10% LIX 84 I is quite large, up to Ceo = 1064 mg/L, the copper extraction rates or vice-versa.
extraction rates appear to be dominated by the loading rates. Extraction at treat ratios of 1: 6, 1:10 and 1:15 were
When Ceo is increased sharply, aspects like stripping, diffusion performed using emulsions containing 10% LIX 84 I as carrier
of the copperoxime complex etc become increasingly and having an internal phase fraction = 0.5. The initial feed
important. In such situations loading alone is not sufficient to concentration was maintained at Ceo 500 mg/L. Fig. 8 shows
sustain the extraction rates as can be seen from the nature of the extraction curves, it is seen that all the curves converge after
extraction curves of 1925 mg/L and 3120 mg/L. In both these 2 min contact indicating same overall extent of extraction but in
cases, 88% extraction is noted in 180 s. the first 90 s of extraction there is considerable difference in the
The lack of similarity between the extraction curves extraction rates for TR = 1:6 and TR = 1:15. Similarly there is a
obtained for case I: Ceo = 928 mg/L, Cc = 5% LIX 84 I in difference in extraction curves for TR = 1:6 and TR = 1:10 but to
Fig. 6 and case II: Ceo = 1925 mg/L, Cc = 10% LIX 84 I in a lesser extent.
Fig. 7 is apparent. Although Ceo and Cc are double in case II The observed difference in extraction rates stem from the
in comparison with case I, even then the two curves do not reduction in loading capacity of the oil membrane, due to
show identity of scale. The difference in the nature of these reduction in the amount of carrier and the oil phase. This effect
extraction curves stem from the greater value of interfacial is even more prominently seen in Fig. 9 that presents the
Fig. 7. Effect of initial copper concentration (Ceo) on rate of copper Fig. 8. Effect of treat ratio (TR) on rate of copper extraction using 10%
extraction using 10% LIX 84 I. ( = 0.5, Wsurf = 3 wt.%, Cio = 1.5 M, LIX 84 I. ( = 0.5, Wsurf = 3 wt.%, Cio = 1.5 M, Cc = 10% v/v,
Cc = 10% v/v, pH = 8.1, TR = 1: 6). pH = 8.1, Ceo 500 mg/L).
B. Sengupta et al. / Hydrometallurgy 89 (2007) 311318 317
Fig. 9. Effect of treat ratio (TR) on rate of copper extraction using 5% Fig. 11. Variation of internal drop size distribution with (Wsurf=3 wt.%,
LIX 84 I. ( = 0.5, Wsurf = 3 wt.%, Cio = 1.5 M, Cc = 5% v/v, pH = 8.1, Cio=1.5 M, Cc=5% v/v).
Ceo 500 mg/L).
5. Conclusions
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Acknowledgements Nathsarma, K.C., Bhaskara Sarma, P.V.R., 1993. Processing of ammo-
niacal solutions containing copper, nickel and cobalt for metal
We would like to thank AICTE, R&D Scheme F. separation. Hydrometallurgy 33, 197210.
No.8021/RID/NPROJ/R&D-2/2002-03 for support to Nilsen, D.N., Siemens, R.E., Rhoads, S.C., 1982. Solvent extraction of
carry out this work, Indian Oil Corporation Limited for nickel and copper from laterite ammoniacal leach liquors. U.S.
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