46  Mineral Processing Technology (MPT 2007)

Optimization of Roasted Sphalerite Concentrate

Leaching Conditions to Dissolve Maximum Amount of
Indium
M. Abdollahy1, A. Khodadadi and M. Karami
Mining Engineering Department, Tarbiat Modarres University, Tehran, Iran
1
E-mail: minmabd@modares.ac.ir

ABSTRACT: Indium (In), atomic number 49 which is part of group 13 in the periodic table, is one of the
strategic metals. In this paper, one and two-step leaching process of roasted sphalerite concentrate in sulfuric acid
to dissolve indium has been investigated and optimum conditions were obtained. In one-step leaching, at first,
optimum leaching conditions with a Taguchi L8 orthogonal array were obtained. The main parameters studied
were: acid concentration (C), temperature (T), time (t) and pulp density (D). Then more precise studies with
alteration of one factor per each experiment method were carried out. In one-step leaching, under conditions C =
5 M, T = 90 °C, t = 3 hr. and D = 100 g/l, 78.7% of indium content in the roasted zinc concentrate, was dissolved.
In two-step leaching, in the initial leaching operation, under conditions C = 1 M, T = 60 °C, t = 1 hr. and D = 100
g/l, more than 90% of zinc and the bulk of other soluble oxides were separated from the indium. About 95% of
indium content of the indium-bearing residue was dissolved under conditions C = 1M, T = 90 °C, t = 3 hr. and D
= 100 g/l. Total recovery of indium in two-step leaching was 96.6%.
Keywords: Roasted Sphalerite Concentrate, Indium, Leaching, Taguchi Method.

1. INTRODUCTION In commercial flow sheet for the production

Indium represents a very minor percentage of the
earth's crust and its concentration is about 0.1
ppm. It does not occur in the native state
(Ullmann’s, 1993).
Indium is classified as a strategic metal. Due
to broad applications of indium in the most new
technologies and its strategic importance, a
significant increased demand is expected. Indium
is highly applicable in electronics, semi-
conductor compounds and photovoltaic devices
(Alfantazi, 2003).
Indium is used in nuclear reactor control-rod
alloys (80% Ag, 15% In, 5% Cd). The consump-
tion of indium in this field was estimated at 3.3
t/a for the replacement of control rods in existing
nuclear power plants in 1986 (Ullmann’s, 1993).
Indium is not mined for itself and sphalerite
(0.5–10000 ppm In) is the most important indium
containing mineral. This metal is always re-
covered as a by-product from extractive circuits of
some base metals such as zinc, lead, tin and
copper (Alfantazi, 2003).
of zinc metal, after having been enriched by
flotation, the sphalerites are roasted to give a zinc
oxide. Such a material could be an important
source of indium, gallium and germanium, which
is leached by sulfuric acid (Gupta and Mukherjee,
1992). Indium and its oxides are soluble in
sulfuric acid, forming indium sulfate (Doran,
1940).
Nowadays, commercial grade indium is
industrially produced using solvent extraction
and cementation technologies from the leach
liquors (Paiva, 2001).
To recover the indium content in (roasted
sphalerite) industrially, one or two leaching steps
are used. One-step leaching is used to leach the
zinc and indium oxides in one stage. In the
process that was developed by Anaconda Copper
Mining Company for leaching and recovery of
indium from zinc calcine, the maximum amount
of indium content in the obtained residue from
the first leaching step, was dissolved in 20 to 25
g/l H2SO4 (Doran, 1940).
47  Mineral Processing Technology (MPT 2007)
In this paper, optimum conditions for indium solution at a given concentration (100/200 g/l
leaching from Bama,s sphalerite concentrate were H2SO4) was poured into the vessel.
investigated using a Taguchi L8 orthogonal array. When desired temperature (60/90 °C) of the
The main investigated parameters in this vessel content was reached, a predetermined
study were: acid concentration (C), temperature amount (10/20 gr) of zinc calcine was added into
(T), time (t), pulp density (D) and stirring rate. the solution while the content of the vessel was
being stirred at a certain speed (700–2000 rpm).
2. MATERIAL AND METHODS At the end of the reaction period, the content of
the vessel was filtered and the filtrate was
50 Kg sphalerite concentrate (under 75 µm) were analyzed by ICP and AAS to determine the
provided from the Bama plant (Irankooh, indium and zinc, respectively. The one-step
Isfahan, Iran) and was divided to about 1 Kg leaching experiments was carried out under
samples using a laboratory sample splitter. Prior mechanical stirring at 900 rpm.
to the dissolution experiments, 50 g samples up
to 2 Kg were roasted in an electrical furnace at
2.1. Taguchi method
950 °C in each run and mixed together. For
complete concentrate characterization, the The technique of defining and investigation all
sample was analyzed using a X-ray diffracto- possible conditions in an experiment involving
meter (Phillips, model EXPERT). The results multiple factors is known as the design of
showed that the raw sample contained mainly experiments. Basically, classical parameter
ZnS, PbSO4, SiO2 and (Ca, Mg)(CO3)2 and the design, which was developed by Fisher, is
roasted concentrate contained mainly ZnO, complicated and not easy to use. In the Taguchi
ZnFe2O4, SiO2 and FeAl2SiO5(OH)2. Major method, special designs of orthogonal arrays are
elements were analyzed using X-ray fluorescence used to study the entire parameter space with a
(XRF) (Phillips, model PW2404). The results small number of experiments only (Roy, 1995).
were given in Table 1. Statistical analysis of variance (ANOVA) was
performed to see whether the process parameters
Table 1: XRF analysis of the sphalerite are statistically significant or not. The F-value for
concentrate and the roasted sphalerite
each process parameter indicates which para-
%w %w meter has a significant effect on the dissolution
Compoun Compoun
d Sphalerit
Roasted d Sphalerit
Roasted value. With ANOVA analysis and performance
e e
characteristic, the optimum combination of
Zn 56.67 67.264 MgO 1.12 1.008
SO3 18.48 5.677 Ba 0.283 0.266
process parameter can be predicted. The
SiO2 11.38 5.248 Pb 0.87 3.257
orthogonal array (OA) L8, which denotes seven
Fe2O3 7.27 6.603 Cu 0.078 0.086 quantities each with two levels, was chosen
CaO 2.09 1.031 P2O5 0.02 which was given in Table 2.
Al2O3 1.82 0.853 LOI 8.5
Table 2: L8 orthogonal array and the results
Elemental indium was analyzed using Parameters and their levels Results
inductively coupled plasma (ICP) spectroscopy Recovery
C T C×T t C×t D
(Varian, model vista-pro ICP-OEP). Zinc was (%)
analyzed using AAS (Phillips, model 9100X). 1 1 1 1 1 1 1 69.9
Analytical sulfuric acid (Merck, Darmstadt, 2 1 1 1 2 2 2 52.3
Germany) and distilled water were used as the 3 1 2 2 1 1 2 59.1
leaching reagent. 4 1 2 2 2 2 1 76.3
The dissolution experiments were performed 5 2 1 2 1 2 2 40.6
in 200 ml open vessel using a hot plate with 6 2 1 2 2 1 1 48.1
mechanical stirrer, a controller unite and a digital 7 2 2 1 1 2 1 68.2
thermometer within (±0.1 °C). 100 ml of acid 8 2 2 1 2 1 2 55.4
Optimization of Roasted Sphalerite Concentrate Leaching… 48
3. ONE-STEP LEACHING Table 5, presented the average of results and
the optimum level for each parameter. As it is
3.1 Determination of Optimum Conditions shown in Table 5, the level of each parameter that
using Taguchi Method has the bigger average of results was chosen as
the optimum level of that parameter.
Acid concentration (C), temperature (T), time (t)
and pulp density (D), were chosen as the main It could be observed that the experiment
effective parameters on the dissolution of indium corresponding to the optimum conditions in
and each in two levels were chosen. Parameters Table 5, has not been performed in the planned
and their levels were presented in Table 3. experimental work in Table 2.
In Taguchi method, if the experiment
Table 3: Parameters and their levels corresponding to the optimum working
Level
conditions was not conducted during the entire
Parameters Level 2 period of the experimental stage, the performance
1
1 Acid concentration (M) 5 7 value corresponding to the optimum working
2 Temperature (°C) 60 90 conditions could be predicted using the following
3 Time (hour) 1 2 formula:
4 Pulp density (g/l) 100 200
T T
Yopt    ( Ai  ) (1)
Table 2 shows the experimental conditions N N
and results for this study based on L8 matrix
Where T is the sum of the results, N is the
design. The results of variance analysis were
given in Table 4. number of results, A i is the average of results
for parameter A that i is its optimum level. The
Table 4: Results of ANOVA analysis confidence interval at the chosen error level
F= 100 × could be calculated using:
parameters f S V = S/f S’
(V/Ve) (S'/ST)
C 1 256.51 256.51 230.2 9.76 22.63
C.I .  ( F (1, n2 )  (Ve N e ) (2)
T 1 289.2 289.2 262.9 11.0 25.84
Where F(1, fe) is the value of the FTable, Ve is
C×T 1 58.86 58.86 32.58 2.24 3.2
the variance of error, and Ne is calculated using:
T 1 4.06 4.06 0.0 0.15 0.0
C×t 1 3.00 3.00 0.0 0.11 0.0 Ne = N/ (1 + n) (3)
D 1 379.5 379.5 353.2 14.4 34.72 Where n is number of degree of freedom
Error 1 26.28 26.28 13.61 used in the prediction of Yopt. Attend to the above
Sum 7 1017.4 100
equations, expected value for maximum recovery
of indium and its confidence interval is
Comparison between standard F (for v1 = 1 calculated:
and v2 = 3, with 90% confidence is 5.5383) and
Yopt = 80.01 ± 5.55
the F-ratio for each parameter in Table 5,
concluded that parameters C, T and D have To test the predicted result, confirmation
significantly meaningful effect for the dissolution experiment was performed under the optimum
of indium. conditions and the recovery of 78.7% was
obtained that is in the calculated range and
Table 5: Average of results for parameters' levels confirmed the statistical results.
Optimum
parameters Level 1 Level 2 L2-L1
level 3.1.1 Alternation of one Factor Per Each
C 64.4 53.1 -11.33 1 (5M) Experiment
T 52.7 64.7 12.03 2 (90 °C)
C×T 61.4 56.1 -5.42 In this section, with emphasis on obtained
t 59.5 58.1 -1.43 1 (1 hour) optimum conditions, using alternation of one
C×t 58.1 59.4 1.23 factor per each experiment method, some of the
D 65.6 51.8 -13.78 1 (100 g/l) parameters were investigated again and new
49  Mineral Processing Technology (MPT 2007)
optimum conditions for stirring rate, acid
concentration and time were determined. In this
case, statistical significance were studied by t-
student test (Hasani Pak, 2000). The
experimental trails and the results were shown in
Table 6.
3.1.2 Effect of Stirring Rate on the
Recovery
To investigate the effect of stirring rate on the
recovery, 4 experiments under optimum
conditions (5 M, 90 °C, 1 hr. and 100 g/l) with 4
different stirring rates were carried out.
Calculated t for the results is 0.331. and tTable
for degree of freedom 3 with 90% confidence, is
2.353 (Hasani Pak, 2000). The calculated t is less
than tTable, so the average of the results in these
experiments is not significantly different from
the Yopt (80.01%), thus the stirring rate with
chosen levels does not have a meaningful effect
on the recovery. Attend to amounts of the
recovery, the stirring rate was adjusted on 1000
rpm for the next experiments.
Table 6: The experiments of the second stage of
two-step leaching
Parameters
Recovery
T D Stirring
C (M) T (°C)
(min) (g/l) (rpm)
5 90 1 100 800
Stirring rate
is 0.551 and is less than tTable (2.353), so the same
as the stirring rate and attend to amounts of the
recovery, the time was adjusted on 3 hour for the
next experiments.
3.1.3 Effect of Acid Concentration on the
Recovery
To investigate the effect of acid concentration on
the recovery, 4 experiments under optimum
conditions (90 °C, 3 hr., 100 g/l and 1000 rpm)
with 4 different acid concentrations were carried
out.
Obtained data were separated in two groups.
So, t was calculated for each group separately.
Calculated t for group 1 (39.3% and 35.7%) is
23.67 and for group 2 (84.8% and 75.2%) is
0.002 and tTable for degree of freedom 1 with 90%
confidence is 3.037 (Hasani Pak, 2000).
In group 1, calculated t (23.67) is bigger than
tTable, so the average of these two data is
significantly different from the Yopt (80.01%),
thus the acid concentration with these levels has
a meaningful effect on the recovery.
In group 2, calculated t (0.002) is less than
tTable, so the average of these two data is not
significantly different from the Yopt (80.01%),
thus the acid concentration with these levels does
(%) not have a meaningful effect on the recovery.
Attend to amounts of the recovery, the 5 M acid
76.6
concentration was confirmed.

5 90 1 100 900 78.7

5 90 1 100 1000 79.9
5 90 1 100 2000 79.9 3.2. Two-step leaching
5 90 1 100 1000 78.7
5 90 2 100 1000 76.3
To dissolve and remove the zinc from the
Time

5 90 3 100 1000 84.8

concentrate, and leave the bulk of the indium in
5 90 4 100 1000 85.1
the residue, under conditions (60°C, 1 hr., 100 g/l
and 800 rpm), 7 experiments on the zinc calcine
Acid concentrationn

0.5 90 3 100 1000 39.3

1.0 90 3 100 1000 35.7
with different acid concentrations were
5 90 3 100 1000 84.8
performed. Table 7 shows the results
The obtained residue from experiments
7 90 3 100 1000 75.2
number 5 and 7, because of the higher amounts
of indium in them, were chosen to continue the
next leaching operation. The majority of zinc and
3.1.2.1. Effect of time on the recovery
other soluble oxides have been dissolved in the
To investigate the effect of time on the recovery, first stage, thus to dissolve the indium content in
4 experiments under optimum conditions (5 M, the residue a very strong acid is not suggested
90°C, 100 g/l and 1000 rpm) with 4 different (Doran, 1940). This was confirmed by the results
time were carried out. Calculated t for the results of performed experiments on the obtained
Optimization of Roasted Sphalerite Concentrate Leaching… 50
residues from experiments number 5 and 7 in indium remained in the residue and was
Table 7. Table 8 shows the results of second stage concentrated. The residue was then dissolved
of leaching operation (leaching of residue). under conditions C = 1 M, T = 90 °C, t = 3
The results showed that about 96.6% of indium hr., D = 100 g/l and stirring rate = 1000 rpm
content in the roasted sphalerite concentrate was and the recovery in this stage was 95%.
dissolved in two steps of leaching with 1 M acid
sulfuric.
Table 8: Second stage of the leaching
Table 7: Primary experiments of two-steps
(leaching of residue)
leaching
Concentratio
Acid Concen- Zinc Indiu n of acid in
Indium in Recovery
concen- trate dissol m Residue the leaching
the (%)
tration dissol- -ution dissol- of residue (g/l
residue H2SO4)
(g/l ution ution
(ppm)
H2SO4) (W %) (%) (%) Indium-bearing residue 49 ------
1 3 3.2 ------ ------ ------ from the initial acid (25
2 10 4.1 ------ ------ ------ g/l H2SO4) leach 98 44
3 15 6.5 ------ ------ ------ Indium-bearing residue 49 68
4 20 11.5 ------ ------ ------ from the initial acid (98
5 25 31.5 27 0.0 73 g/l H2SO4) leach 98 95
6 49 51.6 55 46 50
7 98 77.2 92 33 131
(4) Total recovery of indium in two steps of
leaching with 1 M H2SO4 was about 96.6%.
4. CONCLUSION

The main conclusions can be derived from this REFERENCES

study are as follow:
(1) Maximum recovery of indium in one-step
leaching (84.8%) was obtained under
conditions C = 5 M, T = 90 °C, t = 3 hr., D =
100 g/l and stirring rate = 1000 rpm and the
parameters that had meaningful effect on the
recovery were: acid concentration, time and
pulp density which the latter has the greatest
effect (36.21%).
(2) The predicted and observed dissolution
values were similar to each other, so it may
be concluded that the used array was
adequate to describe the dependence of the
dissolution process on the various parameter.
(3) The bulk of the zinc (90%) and about 33%
of the indium content in the zinc calcine,
under conditions C = 1 M, T = 60°C, t = 1
hr., D = 100 g/l and stirring rate = 800 rpm
was dissolved. In this manner, most of the
[1] Alfantazi, A.M., “Processing of Indium: a
review”, Minerals Engineering, Vol. 16, pp. 687
– 694 (2003).
[2] Doran, H.M., “Recovery of Indium”, 1940, Unite
States Patent: 2384610.
[3] Gupta, C.K., Mukherjee, T.K., “Hydrometallurgy
in Extaction Processes”, Vol. 1, CRC Press,
1992.
[4] Hasani Pak, A.A., "Exploration Data Analysis",
Tehran University Press, Tehran, First Edition,
2000.
[5] Paiva, A.P., “Recovery of indium from aqueous
solutions by solvent extraction”, Separation
Science and Technology, Vol. 36 (7), pp. 1395–
1419 (2001).
[6] Roy, R.K., “A Primer on the Taguchi Method”,
Van Nostrand Reinhold, New York, 1995.
[8] Ullmann’s Encyclopedia of Industrial Chemistry,
“Indium and Indium Compound”, 5th Edition,
Vol. A27, John Wiley & Sons Inc., pp. 157–166
(1993).