J. Min. Metall. Sect. B-Metall.

52 (1) B (2016) 09 - 15 Journal of Mining and Metallurgy,

Section B: Metallurgy

EffEct of Na2co3 oN thE prEparatIoN of MEtallIc tIN froM

caSSItErItE roaStEd uNdEr StroNg rEductIvE atMoSphErE

Y. Zhang*, B. liu, Z. Su, J. chen, g. li, t. Jiang

Central South University, School of Minerals Processing and Bioengineering, Changsha, China

(Received 07 February 2015; accepted 20 December 2015)

Abstract

Tin is an indispensable metal in the modern industry. The current tin smelting processes, however, have the disadvantages
of high smelting temperature, long smelting time, especially high tin loss ratio (>10 wt%). The tin loss attributes to the
volatilization as gaseous SnO and stannous silicate (SnO·SiO2) residual in the slag. An innovative approach for preparing
metallic tin effectively from cassiterite in the presence of Na2CO3, named gas-based reduction roasting followed by water
leaching process, is under development in Central South University, China. The present study, using chemically pure SnO2
and SiO2, aims to determine the impact of Na2CO3 on the metallic tin preparation from cassiterite by the novel process using
XRD, SEM-EDS, chemical analysis, etc. It was found that Na2CO3 effectively restrained the tin volatilization as SnO and
the formation of hardly reductive SnO·SiO2 during the reduction roasting process. In the presence of Na2CO3, most of SnO2
in the raw materials (mixture of SnO2+SiO2) was directly reduced to metallic tin, and part of SnO2 reacted with Na2CO3 to
form intermediate Na2SnO3, which was then reduced to metallic tin. The SiO2 was transformed into Na2SiO3 and then went
into the water solution in the following water-leaching process. The main reactions of the SnO2 + SiO2 system in the
presence of Na2CO3 under reductive atmosphere were ascertained.

Keywords: Stannic oxide; Cassiterite; Reduction roasting; Sodium carbonate; Metallic tin.

1. Introduction wt%~15 wt%. There were two main reasons for the
tin loss: 1) SnO2 could be reduced to intermediate
Tin is one of the earliest applied metals throughout product SnO during the smelting process. The SnO
the human history. In recent decade, the global tin had a larger vapor pressure at higher temperature
production and consumption amounts are in the range (more than 1000 ○C) [9-12], so it was volatilized into
of 300, 000 ~ 400, 000 tons per year [1]. Traditional the fume and dust as the form of gaseous SnO. The
tin smelting processes, including air draught, percent of tin loss in the fume and dust was more than
reverberatory, electric and ausmelt furnaces, as 5 wt% [6]; 2) SiO2 in the pre-treated cassiterite
reported, have the disadvantages of high smelting concentrates would be reacted with SnO to form
temperature, long smelting time, especially high tin stannous silicate (SnO·SiO2). The SnO in the form of
loss ratio (>10 wt%) [2-6]. SnO·SiO2 had low activity coefficient, so this part of
During the production for metallic tin, cassiterite SnO was hardly reduced to metallic tin and then left
concentrates must be pretreated initially by oxidizing in the slag [13-17]. The percent of tin loss in the slag
roasting and hydrochloric acid leaching process to was in the range of 1 wt% ~10 wt% [6, 8]. In the
remove the impurities including sulfur, arsenic, industrial production, limestone was added into the
antimony, iron, lead, manganese, bismuth, tungsten, smelting furnaces because CaO was more easily
etc.. However, the main gangue component, SiO2 combined with SiO2 compared to SnO. Thus, part of
(about 10 wt %), is unable to be effectively wiped off SnO could be liberated from the hardly reductive
[6, 7]. In the subsequent smelting process, slag- SnO·SiO2. The addition of CaO, however, would
making process is required for desilicification by further bring about the rising of the smelting
producing calcium silicate. Therefore, high smelting temperature and increase the volatilization of gaseous
temperature and long smelting time is required for the SnO.
slag-making process smoothly. Extensive studies were carried out using solid
The production practice indicated that the Sn reductive agents (graphite, coke, petroleum coke,
direct recovery of the existing tin smelting processes anthracite, charcoal, coconut etc.) and gaseous
was in the range of 85 wt%~90 wt% [6, 8]. In another reductive agents (CO, H2, CH4) [9, 18-20] to reveal
word, the tin loss in the smelting process was 10 the reduction mechanism of SnO2. Nevertheless, little

* Corresponding author: sintering@[Link]

DOI:10.2298/JMMB150207006Z
10 Y. Zhang et al. / JMM 52 (1) B (2016) 09 - 15

attention was paid to the reduction behaviors of SnO2 (<0.074 mm). The gases used for the reduction
in the presence of sodium salts. One promising but roasting process, including CO, CO2 and N2, were
preindustrial preparation method for metallic tin was more than 99.99 vol% pure.
put forward by V. G. Komkov [21]. In his study, the
physicochemical aspects of carbothermic reduction of 2.2. Methods
cassiterite in the ionic melt were conducted using
cassiterite, sodium nitrate and sodium carbonate as The experimental flow sheet is shown in Fig. 1.
raw materials and low-sulfur coal as reducing agent. The mixture of SnO2 + 10 wt% SiO2 and Na2CO3 were
During the smelting process, NaNO3 (decomposition first mixed in a certain matching ratio. About 5.0 g
temperature 380 ○C) was decomposed into Na2O. The mixture with 10% moisture was agglomerated to be a
new-born alkaline oxide, Na2O, however, was cylindric briquette with 10 mm in diameter and 10mm
detrimental to the operation life of costly refractory in height under the pressure of 10 MPa. The green
materials for the smelting equipments. Furthermore, briquettes were dried in a drying oven at 105 °C for 4
the final decomposition gaseous product, NOx, would h. Then, the experiments were carried out based on
lead to environmental pollution. the following procedure of reduction roasting and
As reported in our previous study, sodium stannate grind-leaching.
(Na2SnO3) is prepared from chemically pure stannic The dried briquettes were placed into a porcelain
oxide [22] (or cassiterite concentrates [23]) and crucible and loaded into a heat resistant quartz glass
sodium carbonate via a weak reduction roasting under tube. The samples were then pushed to the constant
CO/CO2 atmosphere (CO content less than 30 vol %) temperature zone in an electrically heated horizontal
followed by water leaching process. It was tube furnace. Beforehand, the furnace was heated to a
noteworthy to mention that metallic tin began to preset temperature. The roasting temperature was
appear when the mixture of SnO2 and Na2CO3 was measured with a Pt–Rh thermocouple and controlled
roasted at 875 °C for 45 min if the CO content in the using a KSY Intelligent Temperature Controller
mixed CO/CO2 gas exceeded 25 vol%. In the (accuracy ± 5 °C). The experimental schematic diagram
subsequent experiments, crude tin with purity over for reduction roasting is the same as that presented in the
95% and tin direct recovery over 98% was obtained previous study [22]. Pure N2 was introduced into the
when the pretreated cassiterite and Na2CO3 were quartz tube until the temperature reached a constant
roasted under strong reductive atmosphere at high value. Next, the N2 was immediately replaced by the
temperatures. Based on the findings mentioned above, mixed CO/CO2 gas. The content of CO in the CO/CO2
a new technical route to efficiently prepare metallic mixture was adjusted by controlling the flowmeters.
tin from cassiterite and Na2CO3 via a reduction The inlet gas flow was fixed at 4.0 dm3/min. After being
roasting followed by water leaching process is put roasted at given temperatures for certain time, the
forward and has been applied for a Chinese patent roasted briquettes were cooled to room temperature in
[24]. pure N2 atmosphere, and then discharged from the
In order to examine the impact of Na2CO3 on the quartz tube followed by precise weighting and grinding.
recovery of metallic tin from cassiterite by the novel
process, chemically pure SnO2, SiO2 and Na2CO3
were used as research objects in the present work.
Effects of the roasting parameters on the tin direct
recovery were firstly investigated. Then, the phase
transformation, acting mechanism of Na2CO3 and
main reactions during the reduction roasting process
were further determined using XRD, SEM-EDS,
chemical analysis, etc.

2. Experimental
2.1. Materials

SnO2, SiO2 and Na2CO3 used in the study were

analytical grade reagents with purity more than 99.5
wt%. As mentioned above, the percent of SiO2 in the
pretreated cassiterite concentrates before entering into
the smelting furnaces was about 10 wt% [6]. Hence,
10 wt% SiO2 was added into the SnO2 powders served
as raw materials. The tested samples were pre-ground
to a particle size passing through a 200 mesh screen
Figure 1. The experimental flowsheet
 Y. Zhang et al. / JMM 52 (1) B (2016) 09 - 15 11

A computerized X-ray diffraction equipment (XRD, volatilizing into the flue gas [10-12] and the leachable
D/max 2550PC, Japan Rigaku Co., Ltd.) was used to sodium stannate [22, 23] entering into the leaching
determine phase composition of the roasted products. solution in the soda roasting-leaching process would
Some roasted products were also analyzed by the lead to the loss of tin. Therefore, the Sn direct
scanning electron microscope equipped with an energy recovery wasV calculated. in accordance with the
diffraction spectrum (SEM-EDS, JEOL, JSM-6490LV, following expressions:
Japan). m  m2
 = 1 ×100 (2)
After cooling, in each leaching test, 10.0 g of the m1
roasted products was put into a ceramic ball mill for
grind-leaching with hot water. Next, the leaching  (1   %)  
1 (3)
 = ×100
residue and solution were separated by filtering and 
prepared for the determination of metallic tin content C× V
in the residue using chemistry titration and Sn = ×104 (4)
 × m1
concentration in the solution using ICP-AES (ICP-
AES, PS-6, American Baird Co., Ltd.). R = 100     (5)
The main phase in the leaching solution was Where m1 is the mass of the sample before
Na2SiO3 as well as a small amount of Na2SnO3 and reduced, (g); m2 is the mass of the sample after
unreacted Na2CO3. Na2SiO3, Na2CO3 and Na2SnO3 reduced, (g); ε is the weight loss ratio of the sample,
were leachable easily in the water [25, 26]. According (wt%); γ is the tin volatilized fraction, (wt%); δ is the
to our previous study [22], the maximum leaching Sn grade of the sample before reduced, (wt%); α is the
efficiency of tin as the form of Na2SnO3 was obtained Sn grade of the roasted sample (wt%); β is the Sn loss
under the optimal leaching conditions: water-to-solid ratio in leaching solution (wt%); C is the mass
ratio of 4 cm3/g, leaching temperature of 40 °C, concentration of Sn in the leach liquor (g/dm3); V is
leaching time of 45 min and stirring rate of 300 rpm. the volume of the leaching solution (dm3); R is the Sn
Hence, the suitable leaching conditions used in the direct recovery (wt%).
study were chosen as the same as those mentioned
above. 3. results
2.3. Evaluation indexes The effects of main parameters including Na2CO3
dosage, roasting temperature, CO content and roasting
2.3.1. Metallic tin content time on the metallic tin content and Sn direct recovery
Metallic tin content in the leaching residue is were firstly examined. Here, Na2CO3 dosage refers to
detected by way of chemical analysis. About 0.1 g the mass ratio of Na2CO3/(SnO2+SiO2). CO content
sample was weighed and put into a 250 mL conical refers to the CO volume concentration in the mixed CO-
flask; 30 mL FeCl3 solution (80 g/L) were added and CO2 gas (i.e., CO/(CO+CO2)). After roasting, the
vibrated for 60 min; then filtrated and washed. After roasted products were leached under the optimal
that, 20 ml mixture solution of sulphuric acid and conditions abovementioned. The different roasting
phosphoric acid (15 vol% concentrated H2SO4, 15 conditions and corresponding results were listed in
vol% concentrated H3PO4 and 70 vol% deionized Table 1.
water) was added into the filtrate, then, potassium As observed from Table 1, the metallic tin content
dichromate standard solution (2.4518 g/L is increased rapidly with the increase of Na2CO3 dosage,
equivalent to 0.05 mol/L) was applied for the titration indicating that the presence of Na2CO3 was conductive
of the obtained solution, using sodium diphenylami- to the reduction of SnO2. The tin volatilization fraction
nesulfonate (5 g/L) as an indicator. The metallic tin decreased from 1.1 wt% down to 0 wt% with Na2CO3
content of the leaching residual is calculated by the dosage increasing from 0 wt% to 30 wt%. The Sn direct
following formula: recovery decreased slowly from 98.9 wt% down to 94.3
0.05× V0 wt% when the Na2CO3 dosage was 10 wt%. Then, the
 = ×118.69 (1)
40× m0 Sn direct recovery decreased dramatically when the
Where θ is metallic tin content of the leaching Na2CO3 dosage exceeded 10 wt% until it tended to be a
residue, (wt %); 1 V is the potassium dichromate constant at the Na2CO3 dosage of 30 wt%. Thus,
standard solution consumed during the titration, (mL); Na2CO3 dosage of 30 wt% was recommended as the
0

118.69 is the amount of substance of Sn, (g/mol); m0 favorable value in the next experiments.
is the actual weight of ore sample for chemical It is also shown in Table 1 that both the metallic tin
analysis,C(g). content and Sn direct recovery increase markedly as the
= increasing of roasting temperature and time. Based on
2.3.2. Sn direct recovery the results, 950 °C and 120 min were selected to be the
R
The previous studies showed that the SnO suitable roasting temperature and time.
12 Y. Zhang et al. / JMM 52 (1) B (2016) 09 - 15

Table 1. Tin separation and direct recovery from SnO2 + SiO2 under different reduction conditions

Roasting conditions Metallic tin

Volatilized
content in Sn direct
fraction of Sn
Test No. Na2CO3 leaching recovery R
Temp. CO content Time γ
dosage residual θ / wt%
/°C / vol% /min / wt%
/ wt% / wt%
1 0 40.6 1.1 98.9
2 10 42.3 0.4 94.3
3 20 900 50 30 50.2 0.2 76.1
4 30 56 0 71.9
5 40 64.2 0 71.7
6 950 70.5 76.4
50 30 0
7 1000 83.2 79.7
8 60 75.2 69.1
30 950 30 0
9 80 85.2 77.2
10 90 95.2 93.8
950 80 0
11 120 97.3 98.1
12* 30 950 80 120 96.5 0 98.5
* Cassiterite (87.8 wt% SnO2 and 11.0 wt% SiO2) was set as the raw material.

The metallic tin content is enhanced from 56.0 No. 1~5 in Table 1). It can be seen that the
wt% to 85.2 wt% with the increase of CO content diffraction peaks of SiO2 disappeared when Na2CO3
from 50% to 80%. However, the Sn direct recovery dosage exceeded 10 wt%, indicating that SiO2
decreases from 71.9 wt% to 69.1 wt% with increasing nearly completely reacted with Na2CO3 during the
the CO content from 50 vol% to 60 vol%, and then roasting process. From the result of test No. 2, it is
increases to 77.2 wt% when the CO content further inferred that a small amount of leachable Na2SnO3 is
increases to 80 vol%. Hence, the CO content of 80 formed when Na2CO3 dosage is 10 wt%, because
vol% was recommended for the subsequent Na2CO3 was preferentially reacted with SiO2. As the
experiments. Na2CO3 dosage increased more than 20 wt%, there
In test No. 12, cassiterite (87.8 wt% SnO2 and 11.0 were typical diffraction peaks of Na2SnO3 in the
wt% SiO2) was set as the raw material, and 96.5 wt% XRD patterns. The diffraction peak intensity of
crude tin and 98.5 wt% Sn direct recovery were obtained Na2SnO3 enhanced with the increasing of Na2CO3
under the aforementioned optimal roasting conditions.

4. discussion on the effect of Na2co3

A novel process of gas-based reduction roasting

followed by water-leaching for metallic tin
preparation from cassiterite in the presence of Na2CO3
was put forward. By this process, the Sn direct
recovery was increased by 8 wt%~13 wt% compared
with the traditional smelting processes in the absence
of Na2CO3. It is concluded that Na2CO3 has positive
impact on the recovery of tin from cassiterite. Next,
the effect of Na2CO3 was discussed.

4.1. Phase transformation during the reduction

roasting process

4.1.1. Effect of Na2CO3 dosage Figure 2. XRD patterns of the samples roasted at different
Fig. 2 illustrates the XRD patterns of the Na2CO3 dosage (roasting at 900 °C for 30 min
samples roasted with diverse Na2CO3 dosage (Test with 50 vol% CO content).
 Y. Zhang et al. / JMM 52 (1) B (2016) 09 - 15 13

dosage. Because Na2SnO3 was water-soluble, so the

Sn direct recovery was decreased sharply with the
increase of Na2CO3 dosage (shown in the Table 1).
According to Table 1, the tin volatilization
fraction and Sn direct recovery were 1.1 wt% and
98.9 wt% when the mixture of SnO2+SiO2 was
roasted in the absence of Na2CO3. However, the
metallic tin content was only 40.6 wt%. This was
due to the easy formation of hardly reductive
SnO·SiO2 in the system, which is detected by
SEM/EDS and shown in Fig. 3 (roasted product of
test No.1 in Table 1). From Fig. 3, we can see that
spot C in SEM image was SnO·SiO2, which was
characterized by EDS analysis.

Figure 4. XRD patterns of the samples roasted at different

CO contents (roasting at 950 °C for 30 min with
30 wt% Na2CO3 dosage).

4.2. The mechanism of Na2CO3 on improving the

Sn direct recovery

4.2.1. Effect of Na2CO3 on the formation of

stannous silicate
It was reported that silicate stannous was produced
inevitably during the present tin smelting processes
[13-17]. It was also detected by SEM/EDS and shown
in Fig. 3. In order to determine the effect of Na2CO3
on the formation of SnO·SiO2, pure SnO and SiO2
with molar ratio of 1: 1 were roasted at 950 °C for 60
min under 15 vol% CO atmosphere in the absence and
presence of Na2CO3, respectively. Sample 1# was the
product roasted with SnO: SiO2 molar ratio of 1:1 and
sample 2# was the product roasted with SnO:
SiO2:Na2CO3 molar ratio of [Link].
Fig. 5 displays the XRD patterns of the sample 1#
and 2#. It can be seen that a little SnO2 and Sn were

Figure 3. SEM/EDS analysis of the sample roasted in the

absence of Na2CO3 (Test No. 1: roasting at 900
°C for 30 min with 50 vol% CO content).

4.1.2. Effect of CO content

Fig. 4 displays the XRD patterns of the samples
roasted at CO content of 60 vol% and 80 vol% (Test No.
8 and 9 in Table 1). It can be seen that the diffraction
peak intensity of SnO2 and Na2SnO3 decreased while
the diffraction peak intensity of metallic tin increased
with the increase of CO content. This demonstrated that Figure 5. XRD patterns of roasted products of SnO and
new-born Na2SnO3 was again reduced to metallic tin SiO2 in the absence (sample 1#) and presence
under stronger reductive atmosphere. (sample 2#) of Na2CO3 (roasting temperature of
950 °C for 60 min with 15 vol% CO content).
14 Y. Zhang et al. / JMM 52 (1) B (2016) 09 - 15

found in the sample 1# and 2# due to the disproportion the absence of Na2CO3. From the analyses of Figs.
of SnO [9]; the amorphous diffraction peaks in the 2~6, we can confirm that the main phases during the
sample 1# was attributed to SnO·SiO2, which had been reduction roasting for SnO2 in the presence of Na2CO3
identified as stannous silicate [13, 14]. The stannous were Na2CO3, SnO2, Sn, SnO, SnO·SiO2, Na2SiO3,
silicate with low melting temperature (865 °C) [15- Na2SnO3, as well as the gaseous phase CO and CO2.
17] was characterized as hardly reductive tin-bearing
material. However, in the sample 2#, vast Na2SnO3 4.3.1. In the absence of Na2CO3
and Na2SiO3 were found when Na2CO3 was added Combined with the previous researches, the main
into the mixture of SnO and SiO2. It was demonstrated reactions during the reduction roasting for SnO2
that the reaction of SnO and SiO2 was changed without Na2CO3 are summarized and listed as Eqs.
dramatically in the presence of Na2CO3. Hence, the Sn (6)~(9). In the traditional tin smelting process, the
direct recovery was able to be obviously improved volatilization loss of tin derived from the two
due to the inhibition of forming hardly reductive reactions of Eq. (7) and (9). The formation of hardly
SnO·SiO2. reductive SnO·SiO2 was ascribed to Eq. (10).
SnO2 + 2CO = Sn + CO2 (6)
4.2.2. Effect of Na2CO3 on the volatilized fraction
of tin SnO2 + CO = SnO + CO2 (7)
In the tin smelting process, the loss of tin in the SnO + CO = Sn + CO2 (8)
form of SnO(g) must be restrained as much as possible.
Thus, SnO2 and 0 ~ 40 wt% dosage Na2CO3 was SnO2 + Sn = 2SnO (9)
roasted at 950 °C with 15 vol% CO content for 60 SnO + SiO2 = SnO · SiO2 (10)
min. Here, Na2CO3 dosage refers to the mass ratio of
Na2CO3 to SnO2 (i.e., Na2CO3/SnO2). Effect of
4.3.2. In the presence of Na2CO3
Na2CO3 dosage on the tin volatilized fraction is
From Fig. 5, Na2SiO3 formed and SnO·SiO2
determined and the results are plotted in Fig. 6.
disappeared when Na2CO3 was added into the mixture
According to Fig. 6, the tin volatilized fraction
of SnO2 and SiO2 during the reduction process. From
decreases from 2.0 wt% down to 0 wt% continuously
Fig. 6, the volatilization of SnO was restrained in the
with the increase of Na2CO3 dosage from 0 wt% up to
presence of Na2CO3. As shown in Fig. 5, SnO was
40 wt%. It was indicated that Na2CO3 restrained the
able to react with Na2CO3 and form Na2SnO3.
volatilization of SnO. This was the other reason for
Moreover, the reduction of Na2SnO3 to metallic tin
the improvement of the Sn direct recovery.
also existed during the reduction roasting process,
which was observed from Fig. 4. Therefore, besides
Eqs. (6)~(9) existing in the reduction process, some
other reactions, Eqs. (11)~(15), would also take place
in the presence of Na2CO3.
SnO2+Na2CO3=Na2SnO3+CO2 (11)
SnO+Na2CO3=Na2SnO3+CO (12)
Na2SnO3+2CO=Sn+Na2CO3+CO2 (13)
SiO2+Na2CO3=Na2SiO3+CO2 (14)
2Na2CO3+SnO·SiO2= Na2SiO3+ Na2SnO3+CO (15)
In the novel process, the restrained effect of the
volatilization of SnO and formation of SnO·SiO2 were
attributed to the Eqs. (12) and Eqs. (14)~(15),
respectively.
Figure 6. Effect of Na2CO3 dosage on the tin volatilization
fraction (roasting at 950 °C for 60 min with 15 5. conclusions
vol% CO content).
An innovative approach of reduction roasting in
the presence of Na2CO3 followed by water-leaching
4.3. Main reactions during the reduction
process to prepare metallic tin from cassiterite has
roasting process
been developed by the authors’ group. This study
reveals the effect of Na2CO3 on the recovery of tin
The previous studies focused on the reductive
using chemically pure SnO2 and SiO2 as research
reaction of tin oxides under CO/CO2 atmosphere in
 Y. Zhang et al. / JMM 52 (1) B (2016) 09 - 15 15

objects. It was found that Na2CO3 effectively [15] F. He, Z.J. Li, Chemical Metallurgy, 4 (1985) 63-66. (in
restrained the formation of hardly reductive SnO·SiO2 Chinese)
and the volatilization of SnO(g). This was due to the [16] Z.J. Li, A.C. Lu, E.T. Sun, Acta Metallurgica Sinica, 7
formation of Na2SiO3 and intermediate Na2SnO3. (1964) 383-390. (in Chinese)
Then, the intermediate Na2SnO3 was reduced to [17] Z.J. Li, Journal of Kunming University of Science and
Technology (Natural Science Edition), 4 (1979) 1-7. (in
metallic tin at higher temperature under stronger Chinese)
reductive atmosphere during the roasting process. [18] S. Cetinkaya, S. Eroglu, Int. J. Miner. Process. 110–111
Na2SiO3 got into the leaching solution during the (2012) 71–73.
following water-leaching process. As a result, the [19] B.S. Kim, J.C. Lee, H.S. Yoon, S.K. Kim, Materials
metallic tin content and Sn direct recovery of 97.3 Transactions, 9 (2011) 1814-1817.
wt% and 98.1 wt%, respectively, are achieved under [20] R. Padilla, H.Y. Sohn, Metallurgical Transaction B 10B
the optimal experimental conditions: roasting (1979) 109-115.
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roasting time of 120 min and Na2CO3 dosage Journal of Non-Ferrous Metals, 50 (2009) 596–599.
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acknowledgements [23] Y.B. Zhang, Z.J. Su, Z.X. You, B.B. Liu, G. Yang, G.H.
Li, T. Jiang, Rare Metal Technology, Conference
Proceeding, TMS 2014, 163-169.
The authors wish to express their thanks to the
National Natural Science Foundation of China [24] Y.B. Zhang, T. Jiang , G.H. Li, B.B. Liu, Chinese
Patent 201410347188.7.
(51574283), Teachers’ Research Fund of Central
[25] A.L. Chen, Z.W. Zhao, D. Xu, X.-H. Liu, X.-Y. Chen,
South University (2013JSJJ028) and the Hydrometallurgy, 136 (2013) 46-50.
Fundamental Research Funds for the Central [26] M.S. Khan, S.N. Rogak, J. Supercrit. Fluid., 30 (2004)
Universities of Central South University 359-373.
(2014zzts278) for the financial support of this
research.

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