Hydrometallurgy , 32 ( 1993 ) 189-200 189

Elsevier Science Publishers B.V., Amsterdam

Separation by solvent extraction of tellurium ( IV )

and selenium ( IV ) with tri-n butyl phosphate:
some mechanistic aspects
Madhusree Roy Chowdhury and Shyamal K . Sanyal
Department of Chemical Engineering, Jadavpur University , Calcutta 700032 , India
( Received January 9, 1992; revised version accepted April 11 , 1992 )

ABSTRACT

Roy Chowdhury, M. and Sanyal, S. K., 1993. Separation by solvent extraction of tellurium ( IV ) and
selenium ( IV ) with tri-n butyl phosphate. Hydrometallurgy, 32: 189-200.

The mechanism of tellurium separation from selenium in hydrochloric acid media by solvent ex -
traction with tri- n butyl phosphate in kerosene was investigated in a batch -stirred glass cell. The de-
pendence of extraction on acid , metal and extractant concentration and temperature were studied .
The results suggested a "preferred range” for the above parameters with regard to selectivity and
extraction efficiency. Based on the results, extraction equilibria for the two elements were suggested
indicating the extracted species to be TeCl4 ( TBP ) 3 and SeOCl 2 ( TBP ) 2 at 3-5 M initial acid concen -
tration and H 2SeOCl 4 ( TBP ) 2 at 10 M initial acid concentration. The extraction data further showed
that extraction of tellurium was exothermic in nature while that of selenium was endothermic.

INTRODUCTION

Hydrometallurgical extractions of metals from acid leach liquors using tri -

n butyl phosphate ( TBP ) as the extractant have become increasingly impor-
tant in recent years, mainly because of high extraction efficiency and low en-
ergy consumption . Se ( IV ) and Te ( IV ) , two important elements which have
many applications in electronic and metal alloy industries, are at present sep-
arated from anode slime ( the major source of the two elements apart from
their sulphide ores ) , by a pyrometallurgical process which results in low re-
covery of the elements [ 1 ] .
It is well known that TBP can effectively and selectively extract Te ( IV )
from acid leach solution [ 2-4 ] . The mechanism of Te ( IV ) extraction by TBP
was first suggested by Giganov et al . [ 5 ] . They reported different species of
Te ( IV ) formed by TBP at different hydrochloric acid concentrations. Up to
Correspondence to: S.K. Sanyal , Jadavpur University, Department of Chemical Engineering,
Calcutta 700032, India.

0304-386 X / 93 / $06.00 © 1993 Elsevier Science Publishers B. V. All rights reserved .

190 M. ROY CHOWDHURY AND S.K. SANYAL

10 M acid concentration the extracted complex was reported as

- -
[ Te 3TBP xH 20 ] Cl 4. The claim of Giganov et al. [ 5 ] was contradicted by
Shikheeva [ 6 ] . The latter reported that the extracted complex of Te ( IV ) was
-
TeCl 4 TBP at 4-6 M HC1 solution and at higher acid concentrations the sol-
-
vate formed was H2TeCl6 2TBP. Hoh et al. [ 7 ] , while working on the sepa-
ration of Se ( IY ) from Te ( IV ) using 1.1 M TBP in kerosene as extractant ,
reported that a high degree of separation was possible. The maximum loading
capacity, which is very much dependent upon the mechanism of extraction
for 1.1 M TBP was reported to be 9.4 mM for Te ( IV ) . The result was far
lower than the value obtained by Giganov et al. [ 5 ] . The species formed in
-
Se ( IV ) extraction was stated to be H2SeOCl 4 2TBP by Reddy et al. [ 8 ]. Thus,
although these results indicate some useful preliminary knowledge, particu-
larly with regard to tellurium extraction, there is considerable difference in
opinion with regard to the nature of the complex extracted. Moreover, little
information is available with regard to separation behaviour of Te ( IV ) in
association with Se ( IV ) as encountered in extraction from anode slime. The
study of Hoh et al. [ 7 ] indicates the separation behaviour of the two metals,
but their results give no information about the mechanism of extraction .
The present study was undertaken to investigate the effect of various ex-
traction parameters on the extraction and separation behaviour of Se ( IV )
and Te ( IV ) in acid chloride media using TBP as extractant. The mechanism
of extraction and the nature of the extracted complex was sought. Parameters
studied include metal concentration , acid concentration, TBP concentration,
O / A phase ratio and temperature of extraction in order to select the optimum
conditions for separation.

EXPERIMENTAL

Materials

All the chemicals used in this experiment were AR grade. Se ( IV ) and

Te ( IV ) powder of 99.999% purity, obtained from Nuclear Fuel Complex,
Hyderabad, India were used. The metals were dissolved in concentrated hy-
drochloric acid containing nitric acid. The solution was then evaporated to
dryness and the dry salts were dissolved in hydrochloric acid of strength rang-
ing from 1.5 to 10 M .
TBP ( Merck-Schuchardt ) was used after necessary purification [ 9 ]. It was
diluted with commercial kerosene after treatment with 98% sulphuric acid,
neutralization with alkali followed by distillation ( boiling range 140-220 ° C,
density 786 kg / m3 ) . The concentration of the extractant was varied from
0.368 to 3.68 Min the organic phase.
SEPARATION OF Te ( IV ) AND Se ( IV ) WITH TRI -n BUTYL PHOSPHATE 191

Analysis

Se ( IV ) and Te ( IY ) in the aqueous phase were determined by atomic ab-

sorption spectrophotometer ( Perkin Elmer, P-Type 2380 ) . The metal con-
centration in the organic phase was calculated from the difference in concen-
tration in the aqueous phase before and after extraction and was checked from
time to time by scrubbing and stripping a sample of organic phase with 0.5 M
and 5 M hydrochloric acid solution , respectively, and analysing it in the same
way as for the aqueous sample.

Extraction procedure
The extraction runs were carried out in a batch, jacketed, glass mixer of 0.2
1 capacity as shown in Fig. 1. It had arrangements for feed entry and raffinate
outlet. A glass impeller was used for agitation. It was driven by a variable
speed motor and the stirring speed was measured by a strobometer, type E101,
Toshniwal, India. The jacket was connected to an outside constant tempera-
ture circulating bath ( Haake F3 digital ) for temperature control during the
runs and the temperature was maintained within ± 0.1 ° C.

o ~ a
b

—c
- -d
h

C2 O

9
0 0
^
f
Fig. 1. Experimental apparatus. a = variable speed motor; /> = stirrer; r = feed point ; c/ = jacket
inlet ; £> = reactor; /= sample point ; g = jacket outlet; h = thermowell.
192 M. ROY CHOWDHURY AND S.K. SANYAL

In the mixer fresh organic solvent consisting of TBP diluted with kerosene
was introduced first and stirred for a few minutes at 700 min 1 and 303 K. '

Then an equal volume of metal-bearing solution was added at the centre of

the vortex. When the metal concentration in the raffinate stream remained
unchanged with time, the extraction was considered to be at equilibrium.

EXTRACTION THEORY

Extraction of metal from hydrochloric acid solution by TBP, a non-ionic

reagent, occurs by solvation of either the hydrogen ion or the metal ion . Metal
acid species or the metal salt formed due to the reaction ionize very slightly ,
according to Orth et al. [ 10 ]. The reaction involved in TBP extraction, for
very low metal concentrations in the aqueous phase, may be expressed as fol-
lows [ 11 ]:
—
xTBP + yM4 + + ( z 4 y ) H + + zCl ( TBP ) v ( M ) v ( H ) z _ 47( CTjT
^ (1)
[ TBP ) V ( M ),( H ) Z _ 4J, ( C1 ) z ]
Kex (2 )
[ TBP ] A [ M 4 + ] V [ H + ] *- 4'[ Cl - Y
where Kex is the equilibrium constant. The distribution coefficient of the metal
is given by:
y [ ( TBP ) v ( M ) J, ( H ) , _ 4 j, ( Cl ) r ]
An = [ M ] / [ M4 + ] =
.
(3)
[ M4 + ]
This leads to:
[ M ] = yK X [ TBP ] A [ M 4 + HH + ] z 4> [ Cr ] z
“
(4)
'
RESULTS AND DISCUSSION

The distribution coefficient versus metal, acid, TBP concentrations and 0 /

A ( organic to aqueous ) phase ratio were plotted from three sets of experi-
mental data and the slopes were taken for each case. The variation of result is
within 5%.

Extraction isotherm and loading capacity

Equilibrium data of Se ( IV ) and Te ( IV ) individually in the organic phase
against their corresponding feed concentration in the aqueous solution at
constant temperature and at a definite concentration of TBP and acid were
plotted ( Fig. 2 ) . The slope of [ Te ] against [ Te4 + ] was found to be 1 , indi-
cating the extracted species to be monomeric and y = 1. For Se ( IV ) , similarly
the value obtained was nearly 1 at very low metal concentrations.
The loading capacity of the extractant was determined by the repeated con-
SEPARATION OFTe ( IV ) AND Se ( IV ) WITH TRI-n BUTYL PHOSPHATE 193

-1

i i

g1
-2

-2 -1
3
log [ M] i mol dm
Fig. 2. Extraction isotherm. [ TBP ] = 1.1 M\ acid concentration = 4.5 M\ T = 303 K .

tact of organic phase with a fresh feed solution of the metal of same concen-
tration. For a 1.1 M solution of TBP in kerosene at 4.5 M initial acid concen-
tration and a O / A of 1 , the maximum loading capacity for Te ( IV ) was found
to be 0.289 Mat 303 K. This leads to the assumption that the solvation num-
ber is 1.1 / 0.289 = 3.806. For Se ( IV ) , similarly, the maximum loading under
the above mentioned conditions was found to be 0.0047 M , but at 10 Minitial
acid strength, the value obtained was 0.43 M, indicating different extraction
mechanisms at different acid concentrations. Moreover, the large difference
in metal loading at 4.5 M initial acid concentration indicates a higher sepa-
ration factor with increasing difference in Te ( IV ) / Se ( IV ) mole ratio up to
the limit of maximum loading of TBP with Te ( IV ) . This is illustrated in Ta-
ble 1.

Effect of acid concentration

From Fig. 3 it is interesting to note that , although the extraction of Te ( IV )

and Se ( IV ) increases with increasing concentration of acid in the aqueous
phase, there is a maximum in selectivity which was obtained at about 4.5 M
initial acid concentration. The very low extraction of Se ( IV ) below 6 M ini-
tial acid is probably due to the limited solubility of the Se ( IV )-TBP complex
formed in the organic phase. The extraction of Te ( IV ) reached its limit at 5
M acid, which indicates that the preferred range of acid concentration is be-
tween 4 and 5 Mfor the maximum separation of Te ( IV ) from Se ( IV ) . Fur-
194 M. ROY CHOWDHURY AND S. K.. SANYAL

TABLE 1

Effect of molar ratio of metals ( Te IV / Se IV ) on separation factor

Metal concentration in Metal cone, in organic phase Separation

aqueous phase ( M ) (M) factor
Te / Sc
Te Se Te Se
0.016 0.00025 0.0145 0.00022 1.32
0.032 0.00025 0.030 0.0002 3.75
0.112 0.00025 0.105 0.000195 42.86
0.16 0.00025 0.153 0.000195 62.46
0.2 0.00025 0.193 0.000195 78.70

2
o
or

-1
0 0- 5 10
log [ H Cl] , mol dm 3 '

Fig. 3. Effect of initial acid concentration on distribution coefficient and separation factor for
Te ( IV ) and Se ( IV ) . [ TBP ] = 1.1 M; [ Te4 + ] = 0.836 m M ; [ Se4 + ] = 0.0535 m M .

ther, the very low loading capacity of Se ( IV ) by TBP at 4-5 Macid enhanced
the separation factor. Komasawa et al. [ 12 ] had earlier established that , in
the case of simultaneous extraction of two metals with TBP at very low metal
concentration, there is no mutual interference with the individual metal ex-
traction when the extractant is present in large excess, the other conditions
remaining the same. Again, at constant TBP concentration in the organic
phase, the variation in slopes at different ranges of acid concentration indi-
cates the presence of different types of species at different levels of acidity.
For Te ( IV ) at 3-5 Macid , a straight line with a slope of 4 was obtained , thus
SEPARATION OF Te ( IV ) AND Se ( IV ) WITH TRI -n BUTYL PHOSPHATE 195

z = 4. Again for Se ( IV ) at 3-6 M acid , the slope was 2, but at 6-10 M acid , it
was 4. The overall extraction equilibria for Te ( IV ) and Se ( IV ) at 3-5 Macid
concentration may thus be expressed as follows:
xTBP + Te4 + + 4C1
^ ( ( TBP ) v ( TeCU )
~
(5)

*TBP + Se02 + 2C1 ^ ( TBPn^OCb )

+ - (6)
and that for Se ( IV ) at 6-10 Macid concentration may be expressed as:
xTBP + Se02 + + 2H + + 4Cl- ^ ( TBP ) ( H 2 Se0Cl4 )
Y
(7)
It was further observed during the preliminary equilibrium test that the
time to reach equilibrium for Te ( IV ) at 4.5 and 10 M acid concentration was
only a few seconds at 700 min - ' stirrer speed. For Se ( IV ) with 10 Macid the
reaction rate was also of the same order as that of Te ( IV ) , although at 4.5 M
acid level the rate was sluggish, taking 15-20 min to reach equilibrium. This
is probably due to the existence of a different reaction scheme in the extrac-
tion mechanism of Se ( IV ) at different acid levels, which is further corrobo-
rated from the different types of extracted species formed for Se ( IV ) at dif-
ferent acid concentrations.

Effect ofTBP concentration

The extractant TBP is considered to involve co-ordination of the phos-

phoryl group ( P = 0 ) directly to metal [ 10 ] , Figure 4 shows that by increasing
the concentration of TBP the distribution coefficient of both metals in-
creases. However, at higher TBP concentrations, selectivity is not much higher
in comparison with the increase in the extractant concentration. The sharp
increase in viscosity at high TBP concentrations increases the phase separa -
tion time. The results thus point out that 0.736 M ( 20 vol% ) to 1.84 M ( 50
vol% ) TBP may be the optimum range for the separation process. The sol-
vation number for Te ( IV ) was determined by the standard method of slope
analysis at low concentration ofTBP and was found to be nearly 3. In the case
ofSe ( IV ) , the value obtained was 2.3 at 4.5 Macid and 2 at 10 Macid. The
overall reaction equilibrium for Te ( IV ) and Se ( IV ) can then be expressed as
follows at 4.5 Macid concentration:
Te4 + + 4C1- + 3TBP = ( TeCl4 ) ( TBP ) 3 (8)
SeO2 + + 2C1- + 2TBP = ( SeOCl2 ) ( TBP ) 2 (9)
and that for Se ( IV ) at 10 Macid concentration:
SeO2 + + 2H + + 4C1- + 2TBP = ( H2 SeOCl4 ) ( TBPfz ( 10 )
Low extraction of Te ( IV ) at very low ( 0.368 M, i.e., 10 vol% ) concentra-
tions ofTBP was due to the stoichiometric unavailability ofTBP for extract-
196 M. ROY CHOWDHURY AND S. K. SANYAL

O
0

- 05 0 0- 5
3
log [T BP ] , mol dm
Fig. 4. Effect of TBP concentration on distribution coefficient and separation factor for Te ( IV )
and Se ( IV ) ; [ Te4 + ] = 0.836 m M - [ Se4 + ] = 0.0535 m M .

ing Te ( IV ) in the presence of Se ( IV ) in hydrochloric acid medium , since

TBP co-extracts HC1 and water from an aqueous phase [ 13,14 ] , Again, on
increasing the TBP concentration, the distribution coefficient of Se ( IV ) and
Te ( IV ) increases. The major change in the nature of the solvent composition
when the TBP concentration is changed from 10 to 50 vol% TBP is responsi-
ble for the increase in efficiency.
From the overall reaction scheme of Te ( IV ) from eq. ( 8 ) it can be pre-
dicted that the maximum loading capacity should be 1.1 / 3 = 0.367 M; how-
ever the value obtained was 0.289 M . The deviation may be due to the in-
crease in volume of organic phase, the decrease in solubility of extracted
species and the unavailability of “free TBP”, as it also co-extracts HC1. For
Se ( IY ) the observed loading value was lower than expected ( 1.1 / 2 = 0.55 M )
due to the low extractability of TBP for the metal salt formed at 4.5 M acid.
At 10 M acid strength, however, the value was nearer to the expected one,
indicating an increase in solubility of the species extracted.

Effect of organic to aqueous volume ratio

Results of contacting different volume ratios of organic to aqueous phase

are presented in Fig. 5. The data indicate that a preferred O / A phase ratio
exists for the system under study, and this was found to be 1 : 1. This is evident
SEPARATION OF Te ( IV ) AND Se ( IV ) WITH TRI - n BUTYL PHOSPHATE 197

o Te ( IY )
* Se ( IV )
•Te ( IV ) / Se ( IY )
-2
2 3 4 5
0 / A ratio
Fig. 5 . Effect of organic to aqueous volume ratio on distribution coefficient and separation
factor for Te ( IV ) and Se ( IV ) . [ TBP ] = 1.1 A/; initial acid concentration = 4.5 A/; [ Te4 + ] = 0.836
mM - [ Se 4 + ] = 0.0535 mM .

from the sharp increase in the separation factor as well as the distribution
coefficient of Te ( IV ) and Se ( IV ) when the phase ratio ( O / A ) changed from
1 : 10 to 1 : 1. This may simply be due to the unavailability of reagent for metal
extraction and so a crowding effect occurs at low phase ratios.

Effect of temperature

Figure 6 shows the temperature effect on the distribution coefficient of

Te ( IV ) and Se ( IV ) under the experimental conditions. On increasing the
temperature, the distribution coefficient for Te ( IV ) was found to decrease
but that for Se ( IV ) increased.
From Van’t Hoff ’s equation, assuming the chloride ion concentration and
“free TBP” remain constant over the temperature studied , the enthalpy of
extraction of Te ( IV ) and Se ( IV ) was determined:

A H° = — 2.303 /KlOg
/?
A /T
^ {\
Te )
)
= - 26.8 kJ / mol of Te extracted at 4.5 M acid
that for Se ( IV ) is:
198 M . ROY CHOWDHURY AND S. K.. SANYAL

° T e (( I Y )
A Se IV)

2- 5 30 35
1/ * 103 K
T
Fig. 6. Effect of temperature on distribution coefficient for Te ( IV ) and Se ( IV ) . [ TBP ] = 1.1
M : acid concentration = 4.5 M for Te ( IV ) and 6 M for Se ( IV ) ; [ Te4 + ] = 0.836 mM \
[ Se4 + ] = 0.0535 mM .

KlogDs, )
AH ° = + 2.3037?
A( l / T )
= + 19.7 kJ / mol of Se extracted at 6 M acid
This suggests that, at low temperatures, the selectivity increases but solubility
of TBP-metal solvates in the organic phase increases with increasing temper-
ature. Therefore, the ambient temperature range ( 293-303 K ) is the opti-
mum range for separation.

CONCLUSION

The results clearly indicate the effects of a close range of operating para-
meters, such as acid , extractant and metal concentration, O / A ratio and tem -
perature on selectivity and extraction efficiency of the two metals, although
the selectivity varies with metal concentration in the aqueous phase. Further ,
the reaction scheme based on extraction data for the two elements was found
to be different.
The following conclusions were drawn:
( 1 ) The nature of the extracted species for Te ( IV ) and Se ( IV ) , as well as
their solvation number, were as according to eqns. ( 8 ) and ( 9 ) at 4.5 Macid
SEPARATION OF Te ( IV ) AND Se ( IV ) WITH TRI -n BUTYL PHOSPHATE 199

concentration and according to eq. ( 10 ) at higher acid concentrations. The

schemes further indicate that the separation was highly sensitive to acid con-
centration which, in turn , affects not only the distribution coefficient but also
the nature of the extracted species.
( 2 ) The extraction for Te ( IV ) was found to be exothermic while that for
Se ( IV ) was endothermic suggesting a temperature range of 293-303 K for
efficient extraction .

LIST OF SYMBOLS

[ M ] or g
D = distribution coefficient = [ M ] aq at equilibrium
AH 0 = enthalpy of extraction
A e*
'
= equilibrium constant of extraction described in eq . ( 1 )
M = metal
O/ A = organic to aqueous volume ratio
R = gas constant
Se ( IV ) = Selenium ( quadrivalent )
r = temperature
TBP = tri-n butyl phosphate
Te ( IV ) = tellurium ( quadrivalent )
A\ y , z = molecularity of TBP, metal and chloride ion
Superscript

= organic phase
Subscript

M = metal

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