Extraction of thorium from tin slag using

acidic roasting and leaching method

Cite as: AIP Conference Proceedings 2232, 040008 (2020); https://doi.org/10.1063/5.0002176
Published Online: 22 April 2020

E. Prasetyo, Y. I. Supriyatna, F. Bahfie, and K. Trinopiawan

AIP Conference Proceedings 2232, 040008 (2020); https://doi.org/10.1063/5.0002176 2232, 040008

© 2020 Author(s).
Extraction of Thorium from Tin Slag Using Acidic Roasting
and Leaching Method

E Prasetyo1, a), Y I Supriyatna1, F Bahfie1, K Trinopiawan2

1
Research Unit for Mineral Technology, Indonesian Institute of Sciences, Lampung Selatan, Indonesia.
2
Center for Nuclear Minerals Technology, National Nuclear Energy Agency of Indonesia, Jakarta Selatan,
Indonesia.
a)
Corresponding e-mail: enriquexploreur@gmail.com

Abstract. Slag as the secondary product (waste) of tin smelter still contains not only valuable elements e.g. rare earth
elements but also radioactive such as Th. Both radioactive elements are accumulated in the slag phase since the raw
materials used in smelting i.e. cassiterite minerals, is closely associated with Th and U containing monazite. Due to valuable
element content, the slag becomes major of interest in mineral processing industries, hence the slag needs to be
decontaminated before it could be processed further. The common approach to reducing Th content from the slag using the
leaching process is considered ineffective due to association of Th with refractory phase e.g. SiO2 and TiO2 in the slag. To
break down the refractory phases, the roasting approach by using the fusing agent is required to release Th so that they
could be leached out using mild lixiviant. In this research, potassium hydrogen sulfate (KHSO4) and sulfuric acid were
used as a fusing agent and lixiviant, respectively. The parameters studied include the molar ratio between fusing agent and
refractory elements in slag, roasting temperature, roasting time, sulfuric acid concentration in lixiviant and pulp density
during the leaching stage. The studies so far demonstrated that optimum condition in Th removal occurred at roasting
temperature 400 ℃, roasting time 2 hours, the molar ratio of potassium hydrogen sulfate to tin slag is 5:1, sulfuric acid
concentration 2 M and pulp density 15 mL/gr.

INTRODUCTION
Thorium (Th) is radioactive elements with a negative effect on the environment and human health, which had been
extensively documented including its deteriorating effect to kidney, brain, lung and heart [1-3]. Several activities had
been known to cause the release of both elements into the environment such as mining and mineral processing [4, 5].
One of mining and mineral processing, which is closely associated with Th and U are the tin placer mining. In tin
placer deposit, the tin mineral is found together with other minerals such as monazite, and xenotime which might
contain Th. Before cassiterite could be processed further to produce tin metal by smelting process, the cassiterite
mineral had to be separated from gangue (undesirable) mineral e.g. quartz and silicate.
Cassiterite concentrate containing trace Th-U minerals would be smelted. During smelting, cassiterite would be
reduced into molten tin metal, while other components such as silicon, titanium and iron including a trace of Th would
be transformed into separate phase i.e. tin slag. This phase is generally considered as waste. The tin slag still contains
valuable elements e.g. rare earth elements, niobium and tantalum [6-9]. Due to its attractive economical value, thus
the decontamination process is considered mandatory. Hence, in this research, Th and U recovery from tin slag would
be studied using roasting followed by leaching process. There are two metallurgical approaches to recover valuable
metals from slag: pyrometallurgy and hydrometallurgy. In the pyrometallurgical process [10-11] the disadvantage
includes high energy consumption and only viable to handle high-grade raw materials. The second approach,
hydrometallurgy [12-15], uses toxic and corrosive chemical dissolution technique to recover the element of interest
(leaching) such as hydrofluoric acid.

Proceedings of the 3rd International Seminar on Metallurgy and Materials (ISMM2019)

AIP Conf. Proc. 2232, 040008-1–040008-6; https://doi.org/10.1063/5.0002176
Published by AIP Publishing. 978-0-7354-1991-9/$30.00

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 Another approach is by combining pyrometallurgy and hydrometallurgy, which is roasting followed by leaching.
In the roasting process, tin slag is mixed with a fusion agent, which function is to transform insoluble-refractory phase
in the tin slag into the soluble phase in the leaching process releasing the target elements. The process is generally
done in relatively lower temperature compared to smelting temperature. The fusion agent had been tested so far
included sodium hydroxide (NaOH) by Trinopiawan et al. [8]. The disadvantage of using NaOH as a fusing agent
(caustic fusion) was the excessive use of acid to neutralize the basic roasting product and high fusion temperature.
These disadvantages inspired to explore other fusion agents to reduce roasting temperature and acid consumption in
the leaching stage. Potassium hydrogen sulfate (KHSO4) would be proposed in this research due to the lower melting
point (200 ℃). The efficacy of potassium hydrogen sulfate as fusion agent to release Th in tin slag decontamination
would be investigated in this research in terms of molar ratio between refractory phases and fusion agent, roasting
temperature, roasting time, sulfuric acid concentration and pulp density in subsequent leaching stage.

MATERIALS AND METHOD

Tin slag sample was obtained from PT Timah. Black and glassy slag were crushed and sieved to an obtained
particle size less than 150 mesh (74 microns). Before used, the sieved tin slag was dried in an electric oven at 120 ℃
for 12 hours. Chemicals used, potassium hydrogen sulfate and sulfuric acid was obtained from Merck, Darmstadt,
Germany and used as received. In the roasting experiment, tin slag was mixed with fusion agent in nickel crucible and
was introduced into muffle furnace. If the heating had been reached the desired temperature, the temperature was kept
constant during predetermined roasting time. The roasting product was then leached using sulfuric acid with varied
concentration and volume for 12 hours. The leaching residue was separated from the supernatant phase and the residue
was then washed with Milli Q water and dried. The Th content in the residue was analyzed using high-resolution XRF
(Panalaytical X'Pert 3 Powder with Omnian Standard). The recovery (R) of Th (decontamination) was calculated
using equation 1:

ሺ஼బ ି஼ಶ ሻൈଵ଴଴Ψ

ܴሺΨሻ ൌ (1)
஼బ

Where C0 and CE were a metal concentration in tin slag before and after treatment (roasting-leaching), respectively.

RESULTS AND DISCUSSION

Tin Slag Characterization

Tin slag characterization using XRF revealed its major components as shown in Table 1. The results showed that
the major components include SiO2 (29 %), CaO (19.5 %), TiO2 (13.5 %) and Al2O3 (11.8 %). Th (ThO2) content in
the tin slag was 0.36%. Characterization using XRD revealed the amorphous nature of tin slag, as shown in Fig. 1.

FIGURE 1. XRD characterization of tin slag, showing no peaks (amorphous material).

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 TABLE 1. Tin slag component before and after leaching treatment (without roasting). L/E is Leached (-) and Enriched (+)
fraction of each phase, respectively. Leaching condition: leaching agent sulfuric acid 2 M, pulp density 20 mL/g, leaching time
12 hours.
Phase Before Leaching (%) After Leaching (%) L/E (%)
Al2O3 11.84 4.51 -61.9
CaO 19.55 22.71 16.2
Cr2O3 0.54 0.32 -40.8
Fe2O3 7.27 4.50 -38.1
K 2O 0.42 0.21 -49.5
MnO 0.71 0.47 -33.8
Nd2O3 0.76 0.57 -24.3
P2O5 0.78 0.10 -87.00
SiO2 29.32 19.01 -35.2
SnO2 1.57 0.76 -51.2
ThO2 0.36 0.29 -18.7
TiO2 13.53 10.23 -24.4
V 2O 5 0.29 0.24 -18.2
Y 2O 3 0.84 0.66 -21.7
ZrO2 8.50 7.74 -9.0

Effect of Fusing Agent Molar Ratio

The effect of the mass ratio of fusing agent added to the tin slag to the Th recovery was studied from 1 to 6. The
constant variable in this study included the roasting temperature of 400 ℃ and roasting time 3 hours. Leaching was
carried out on the roasting product for 12 hours using sulfuric acid 1 M, with pulp density 5 mL/gr. The correlation
between fusing molar ratio to the Th recovery is shown in Fig. 2.

50
45
40
35
Recovery (%)

30
25
20
15
10
5
0
1 2 3 4 5 6
Mass ratio

FIGURE 2. Effect of mass ratio of potassium hydrogen sulfate/tin slag to the recovery of Th.

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 Effect of Roasting Temperature
The effect of roasting temperature to the tin slag decontamination from Th was investigated at 400, 500, 600 and
700 ℃, which results are shown in Fig. 3. The constant variables in this temperature effect study were mass ratio 5,
roasting time 3 hours, while constant leaching parameters were sulfuric acid 1 M, pulp density 5 mL/gr and leaching
time 12 hours.

FIGURE 3. Effect of roasting temperature pre-treatment to the recovery of Th.

Effect of Roasting Time

The effect of roasting time was studied for 2, 3, and 4 hours duration at 400 ℃. Other constant variable included
molar ratio 5, leaching using sulfuric acid 1 M, pulp density 5 mL/gram and 12 hours agitation. The results are shown
in Fig. 4, which shows that the recovery decrease when the roasting time was extended from 2 to 3 hours and increased
back if the roasting time was prolonged to 4 hours.

FIGURE 4. The effect of roasting time to the recovery of Th.

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 The Effect of Sulfuric Acid Concentration as Leaching Agent
The effect of sulfuric acid as leaching agent in Th and U removal from tin slag was studied at constant variable
roasting temperature 400 °C, molar ratio 5 and pulp density 5 ml/gr and leaching time 12, while sulfuric acid
concentration was varied between 1 and 5 M. The results are shown in Fig. 5.

FIGURE 5. The effect of sulfuric acid concentration in leaching agent on Th.

The Effect of Pulp Density in Leaching Stage

The effect of pulp density to recovering Th and U in tin slag after roasting pre-treatment was studied by varying
the leaching agent volume from 5 to 20 mL, which was equilibrated with 1 gr of roasted tin slag (5 to 20 mL/gr). The
constant variable in this study included roasting temperature 400 ℃, molar ratio 5, roasting time 3 hours. During
leaching sulfuric acid concentration and leaching time were kept constant at 2 M and 12 hours, respectively, while the
results are depicted in Fig. 6.

FIGURE 6. The effect of pulp density on the recovery of Th.

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 CONCLUSIONS
The decontamination of tin slag from Th had been carried out using roasting pre-treatment which was followed by
leaching. Potassium hydrogen sulfate had successfully transformed the refractory phase into the soluble phase,
releasing Th. The optimum condition for the recovery of Th were roasting temperature 400 ℃, roasting time 2 hours,
the molar ratio of potassium hydrogen sulfate to tin slag 5, sulfuric acid concentration 2 M and pulp density 15 mL/gr.

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