Minerals Engineering 143 (2019) 105945

Contents lists available at ScienceDirect

Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Innovative methodology for comprehensive use of tin anode slime: T

Preparation of CaSnO3
⁎
Wei Liua,1, Kunhong Gua,1, Junwei Hana,b, , Zhenyu Oua, Dixiu Wua, Deqiang Zhaoc,d,
Wenqing Qina,b
a
School of Minerals Processing and Bioengineering, Central South University, 410083 Changsha, Hunan, China
b
Key Laboratory of Hunan Province for Clean and Efficient Utilization of Strategic Calcium-containing Mineral Resources, Central South University, Changsha 410083,
China
c
Department of Chemical Engineering, University College London, Torrington Place, London WC1E 7JE, UK
d
Key Laboratory of Three Gorges Reservoir Region's Eco-Environment Ministry of Education and National Centre for International Research of Low-carbon and Green
Buildings, Chongqing University, Chongqing 400067, China

A R T I C LE I N FO A B S T R A C T

Keywords: Tin anode slime, a secondary resource containing Sn, was used as a raw material in the preparation of CaSnO3
Alkaline leaching via the processes of soda roasting, alkaline leaching, and precipitation. The effects of roasting, leaching, and
Calcium stannate precipitation on the extraction of tin from slime were investigated in detail. The following optimum conditions
Precipitation were identified: Na2CO3/tin anode slime mass ratio of 1:1, roasting temperature of 1000 °C, roasting time of
Soda roasting
45 min, charcoal powder dosage of 20%, NaOH concentration of 2 mol/L, liquid-to-solid ratio of 14:1, leaching
Tin anode slime
temperature of 65 °C, leaching time of 90 min, CaO/Sn mole ratio of 3.5:1, precipitation temperature of 85 °C,
and precipitation time of 120 min. Under these conditions, more than 95% of Sn was extracted from tin anode
slime after roasting and leaching, in which Sn was converted into Na2SnO3, which enhanced Sn extraction.
Furthermore, more than 99% of Sn was precipitated from the leach solution via the reaction with CaO. The
proposed method exhibits advantages of low pollution, low cost, and high leaching rate, when compared with
the conventional preparation of CaSnO3 or treatment of tin anode slime.

1. Introduction temperature (1300–1500 °C) (Berbenni et al., 2015; Junploy et al.,

CaSnO3 is extensively used as a raw material in many applications,
such as transparent conducting films, environmental monitoring, bio-
chemical sensors, lithium rechargeable batteries, and dye-sensitised
solar cells. CaSnO3 has attracted considerable interest as an n-type
semiconductor owing to its wide energy gap (4.3 eV) (Moshtaghia et al.,
2015; Zhang et al., 2017). Economic development has led to a con-
tinuous increase in the demand for CaSnO3. In 2015, the electronic
solder, chemical, and tinplate industries accounted for 43.5%, 15.5%,
and 14.7%, respectively, of the global Sn consumption (Su et al., 2017b;
Zhao et al., 2017). Moreover, the demand for CaSnO3 has increased
greatly in recent years as the conventional flame retardant, Sb2O3, is
gradually being replaced by stannates (Zhang et al., 2014a,b; Karabulut
et al., 2014; Mouyane et al., 2011).
The common technology for the synthesis of CaSnO3 entails the use
of cassiterite concentrate as the raw material, which is roasted at a high
2018; Zhang et al., 2018; Redfern et al., 2011; Zhang et al., 2011).
Other methods, such as the peroxide precursor, solvothermal and hy-
drothermal, sol-gel, co-precipitation, and polymeric precursor methods
(Moshtaghi et al., 2017; Shi et al., 2017; Maul et al., 2016; Rezainik,
2009; Fan et al., 2007; Su et al., 2017a), show some disadvantages. The
sol-gel and polymeric precursor methods entail the use of expensive and
environmentally harmful reactants. Other methods entailing thermal
treatments of the reactive mixture at high temperatures often result in
excessive grain growth and lack of homogeneity in terms of both par-
ticle size and composition. Thus far, the majority of metallic Sn and tin
chemical products are manufactured using cassiterite through the
process of pyrometallurgical reduction smelting. However, placer de-
posits of Sn have been nearly exhausted following several years of ex-
ploitation. Hence, a suitable replacement for cassiterite needs to be
discovered.
As a by-product from the Sn electrorefining industry, tin anode

⁎
Corresponding author at: School of Minerals Processing and Bioengineering, Central South University, 410083 Changsha, Hunan, China.
E-mail address: hanjunwei@csu.edu.cn (J. Han).
1
W.L. and K.G. contributed equally to this work.

https://doi.org/10.1016/j.mineng.2019.105945
Received 11 December 2018; Received in revised form 18 August 2019; Accepted 19 August 2019
Available online 22 August 2019
0892-6875/ © 2019 Elsevier Ltd. All rights reserved.
W. Liu, et al. Minerals Engineering 143 (2019) 105945

slime is a mixture of Sn, Sb, Bi and other metals deposited on the

bottom of the refining tank during the process of electrolytic refining.
This product is economically attractive and is considered to be one of
the important raw materials for Sn extraction (Han et al., 2017;
Steinlechner, 2018; Xu et al., 2016). At present, the main steps in the
treatment of tin anode slime are pre-treatment, concentration, and re-
fining. Pre-treatment is the most important step and includes the fol-
lowing treatment methods: oxidation roasting-acid leaching (Havuz
et al., 2010; Li et al., 2015; Huang et al., 2016), beneficiation-me-
tallurgy combination (Cao et al., 2010; Han et al., 2015; Su et al., 2016;
Han et al., 2016), reduction smelting electrolysis (Liu et al., 2019), and
vacuum carbothermal reduction (Henao et al., 2015). The use of cas-
siterite to prepare CaSnO3 and the treatment of tin anode slime present
many problems, such as low recovery rate, serious secondary pollution,
high energy consumption, and difficulties in the separation of Sn from
other metals.
Thus far, Sn-bearing wastes have not been used as raw materials to
prepare CaSnO3. In the current study, we aim to develop a new method Fig. 1. XRD patterns of tin anode slime and leaching residue.
for recycling tin anode slime, a secondary Sn resource, to prepare
CaSnO3. After Sn is extracted from tin anode slime, the residue contains
significant quantities of Sb and Bi and can therefore be reused as a raw Bi2O3 (16.48%), some metallic Bi (0.05%), and sulfides (3.12%). The
material for recycling Sb and Bi via Na2S leaching and NaCl-H2SO4 reductant used in the process of roasting was charcoal powder.
leaching, respectively. In this work, we studied the recovery of metal
impurities, mainly Sn, from tin anode slime generated by the tin elec- 2.2. Experimental set-up and procedure
trorefining industry. The effects of the operating parameters of roasting,
leaching, and precipitation on the conversion of Sn contained in tin The schematic diagram of the experimental set-up is shown in
anode slime to CaSnO3 were investigated in detail. The phase trans- Fig. 3. The samples were first ground to −150 mesh, dried in an oven,
formations during the process were also studied. and stored for subsequent experiments. For each test, 10 g of tin anode
slime was thoroughly mixed with a predetermined amount of Na2CO3
using a mortar and pestle. The mixture prepared was placed in a por-
2. Experimental
celain boat, 50 mL in volume (size: 60 mm × 90 mm), which was placed
in a muff furnace for roasting. The samples were heated at the rate of
2.1. Materials
30℃/min to the required temperature and roasted at that temperature
for a certain duration. Upon completion of roasting, the samples were
The tin anode slime used in this study was collected from a smelter
withdrawn after they had cooled to a temperature lower than 100 °C.
in Hunan province, China. The sample was first ground into powder,
Finally, the roasted samples were weighed and ground for analysis and
dried at 75 °C, and sieved to −150 mesh (Li et al., 2013). The sample
leaching tests.
powder was thoroughly mixed for analysis and subsequent experiments.
The leaching experiments were performed in a 500 mL glass beaker,
The main chemical constituents of the sample were determined via
equipped with mechanical stirring, in a thermostatic water bath. Prior
inductively coupled plasma-optical emission spectrometry (ICP-OES;
to leaching, an NaOH solution was prepared in a predetermined con-
ThermoFisher Scientific iCAP 7200 ICP-OES). The results are shown in
centration and liquid-to-solid ratio, placed in the beaker, and heated
Table 1. The tin anode slime contains 30.26% Sn, indicating the high
with stirring at 300 rpm. When the required temperature was reached,
economic value of the recovery of Sn from this material. The crystalline
20 g of the roasted sample was placed in the beaker. After leaching, the
phase composition of the tin anode slime was characterised using X-ray
leaching residue was separated from the leachate via filtration. The
diffraction (XRD; Rigaku Rapid IIR). The result is presented in Fig. 1.
filtrate was collected for the subsequent precipitation experiments,
The XRD pattern of the leaching residue is also presented in Fig. 1. It
while the residue was dried, weighed, and analysed via ICP. In the
can be seen that Sn is present mainly in the form of SnO2. The micro-
precipitation experiments, a required amount of CaO was introduced to
structure of the tin anode slime was also analysed via optical micro-
the filtrate for the precipitation of Sn as CaSnO3·3H2O. Each leaching
scopy and scanning electron microscopy coupled with energy dispersive
test was conducted at least three times and the mean value was used as
spectroscopy (SEM-EDS). The results are shown in Fig. 2. It can be seen
the final results. The standard deviation for each test was calculated and
from Fig. 2 that Sn, Sb, and Bi were closely combined, which explains
presented as the error bars.
the difficulty inherent in the separation of Sn from tin anode slime using
conventional methods. The main metal contents of the different species
in the tin anode slime are given in Table 2. The results indicate that the 2.3. Technical indicators
Sn contained in the slime is primarily distributed in cassiterite, varla-
moffite, silicates, and sulfides. At the same time, it can be seen from In this study, we use two technical indicators to evaluate the ex-
Table 2 that the sample contains 13.3% of Sb and 19.65% of Bi in ad- perimental process: leaching rate (ξL , %) and recovery rate (ηR , %).
dition to a significant quantity of Sn. Sb in the slime is distributed Minitial Winitial − Mfinal Wfinal
mainly in Sb2O3 (8.55%), some metallic Sb (1.03%), sulfides (0.23%), ξL (%) = × 100%,
Minitial Winitial (1)
and unknown phases (3.49%). Bi in the slime is distributed mainly in
Mre cov ery Wre cov ery
ηR (%) = × 100%,
Table 1 Minitial Winitial (2)
Main chemical composition of the tin anode slime.
where Minitial and Mfinal are the masses of the sample before and after
Composition Sn As Sb Bi Pb Cu
leaching, respectively; Winitial and Wfinal are Sn contents of the sample
wt.% 30.26 2.44 13.24 19.38 1.55 2.54 before and after leaching, respectively; Mre cov ery is mass of product; and
Wre cov ery is Sn content of the product.

2
W. Liu, et al. Minerals Engineering 143 (2019) 105945

Fig. 2. SEM-EDS results of tin anode slime.

Table 2 ratio of 1:1. When the mass ratio exceeds 1:1, the raw material sticks to
Main metal content in different species of the tin anode slime. the small pieces owing to excessive alkalinity, thereby impeding the
Metals Species Content (wt.%) process of leaching. Therefore, the leaching rate decreases as the mass
ratio increases from 1:1 to 6:5.
Sn Cassiterite (SnO2) 26.76 As shown in Fig. 4(b), the leaching rate of Sn significantly increases
Varlamoffite (SnO2·xFe2O3·yH2O) 1.93
from 36.12% to 92.55% as the roasting temperature increases from
Silicates (SnO2·xSiO2) 0.36
Sulfides (SnS2) 1.16
600 °C to 900 °C and thereafter gradually reaches a maximum of
Total 30.21 95.25% at 1000 °C. Beyond 1000 °C, the leaching rate exhibits no sig-
Sb Antimony trioxide (Sb2O3) 8.55
nificant change with further increase in temperature.
Metallic antimony (Sb) 1.03 Fig. 4(c) shows that the leaching rate of Sn is 91.94% when the
sulfides (Sb2S3) 0.23 roasting time is 15 min. The rate remarkably increases with roasting
Uncertain phase 3.49 time in the range 15–45 min. Thereafter, the leaching rate increases
Total 13.30
slightly with roasting time and reaches its maximum at 90 min of
Bi Bismuth trioxide (Bi2O3) 16.48 roasting. Considering the energy consumption and leaching rate, the
Metallic bismuth (Bi) 0.05
optimum roasting time is determined to be 45 min.
Sulfides (Bi2S3) 3.12
Total 19.65
As shown in Fig. 4(d), the leaching rate of Sn significantly increases
initially and thereafter gradually reaches the maximum when the do-
sage of charcoal powder is 20%. However, it decreases thereafter with
3. Results and discussion further increase in charcoal powder dosage; this is attributed to the
significant generation of CO, which reduces some SnO2 to metallic Sn
3.1. Soda roasting of tin anode slime during roasting.
Based on the experimental results, the optimum roasting conditions
According to the phase and chemical composition analyses, Sn in were established as follows: Na2CO3/tin anode slime mass ratio of 1:1,
the anode slime is mainly in the form of SnO2. The objective of roasting roasting temperature of 1000 °C, roasting time of 45 min, and charcoal
is to enhance the reaction occurrence of SnO2 and Na2CO3. The main powder dosage of 20%.
chemical reaction in the process of roasting is presented in Eq. (3). The The effects of different roasting conditions on the phase transfor-
effects of the roasting conditions, including Na2CO3/tin anode slime mations were investigated, and the results are shown in Fig. 5. Fig. 5(a)
mass ratio, roasting temperature, roasting time, and amount of charcoal shows the XRD patterns of the samples roasted at different mass ratios
powder additive, on the leaching rate of Sn were investigated. The in- of Na2CO3/tin anode slime. After roasting, the tin anode slime still
itial leaching conditions were fixed as follows: liquid-to-solid ratio of contains mainly SnO2 and a few intermediates with undetermined
10:1, leaching temperature of 85 °C, NaOH concentration of 2 mol/L, phases when the mass ratio is 0 or 2:5. Most of the SnO2 is converted
and leaching time of 120 min. into Na2SnO3 upon roasting when the mass ratio is 9:10 or 6:5. As
shown in Fig. 5(b), the peaks of Na2SnO3 are not observed in the XRD
SnO2 + Na2 CO3 = Na2 SnO3 + CO2 (3)
patterns at 600 °C and the roasted anode slime is mainly composed of
Fig. 4(a) shows that the leaching rate of Sn exhibits no significant SnO2 and Na2CO3, indicating that the reaction between the two hardly
change with increase in Na2CO3/tin anode slime mass ratio in the initial occurred. The peaks of Na2SnO3 appear alongside the decrease in the
period. However, when the mass ratio is varied from 2:5 to 7:10, the intensity of SnO2 peaks as the temperature is increased to 800 °C. The
leaching rate of Sn increases rapidly. The increase in leaching rate is peaks of SnO2 and Na2CO3 disappear when the temperature exceeds
relatively stable and gradually reaches a maximum of 95.49% at a mass

3
W. Liu, et al. Minerals Engineering 143 (2019) 105945

Fig. 3. Schematic diagram of the experimental setup.

1000 °C, implying that the reaction of SnO2 to Na2SnO3 is complete.
Fig. 5(c) indicates that the sample is mainly composed of Na2SnO3
after roasting for 15 min, and increasing the roasting time favours the
formation of Na2SnO3 crystals. The initial impression is that the addi-
tion of charcoal powder has no significant effect on the transformation
of SnO2 to Na2SnO3, as seen from Fig. 5(d). However, it is seen from
Fig. 4(d) that the leaching rate of Sn is only 87.87% after roasting
without charcoal powder but reaches 95.26% after roasting with the
addition of 20% charcoal powder. The effect of C addition on the
transformation of SnO2 to Na2SnO3 is explained as follows. Based on the
experimental results and the literature (Kocemba and Rynkowski, 2011;
Liu et al., 2016a,b, 2017; Zhang et al., 2016), it is concluded that the
CO generated from C during roasting can enhance the reaction between
SnO2 and Na2CO3 to produce Na2SnO3, and this mechanism is depicted

Fig. 4. Effects of roasting conditions: (a) Na2CO3/tin anode slime mass ratio (1000 °C, 45 min, 20% of charcoal powder), (b) roasting temperature (45 min, 20%
charcoal powder, Na2CO3/tin anode slime mass ratio of 1), (c) roasting time (1000 °C, Na2CO3/tin anode slime mass ratio of 1, 20% charcoal powder), and (d)
charcoal powder addition (1000 °C, 45 min, Na2CO3/tin anode slime mass ratio of 1).

4
W. Liu, et al. Minerals Engineering 143 (2019) 105945

Fig. 5. XRD patterns of the samples roasted under various conditions: (a) different Na2CO3/tin anode slime mass ratio, (b) different temperatures, (c) at different
times, (d) different charcoal powder addition (a-Na2SnO3, b-SnO2, c-Na2CO3).

Fig. 6. Reaction mechanism of SnO2 and Na2CO3during the roasting process.

in Fig. 6. A coordinating oxygen anion on the outermost atomic layer of
SnO2 is called ‘bridging oxygen’, which occupies the bridging position
between six coordinated tin cations located in the second layer. The
formation mechanism of the bridging oxygen is expressed using Eqs. (4)
and (5). The removal of the bridging oxygen from the surface creates
one bridging vacancy per unit cell. In this case, the surface of SnO2 with
reduced bridging oxygen anions is in an unstable state, i.e., the removal
of the bridging oxygen weakens the chemical stability of SnO2. At the
same time, the CO molecules in the SnO2-Na2CO3 system roasted in a
CO-CO2 atmosphere have the ability to capture oxygen anions, and

5
W. Liu, et al. Minerals Engineering 143 (2019) 105945

Table 3 reagent consumption and leaching rate, 2 mol/L was regarded as the
Main metal content in different species of the roasting product. optimum NaOH concentration and was used for further experiments.
Metals Species Content (wt.%) Fig. 7(b) shows the effect of liquid-to-solid ratio on the extraction of
Sn. The leaching rate significantly increases as the liquid-to-solid ratio
Sn Cassiterite (SnO2) 0.55 is increased from 4:1 to 6:1, beyond which the rate increases gradually
Sodium stannate (Na2SnO3) 20.45
and reaches its maximum (95.63%) at a liquid-to-solid ratio of 14:1.
Silicates (SnO2·xSiO2) 0.05
Sulfides (SnS2) 0.20
Thereafter, the leaching rate of Sn exhibits no significant change with
Total 21.25 further increase in the liquid-to-solid ratio. As a result, 14:1 was de-
Sb Sodium antimonate (NaSbO3) 9.14
termined to be the optimum liquid-to-solid ratio.
Metallic antimony (Sb) 0.14 Fig. 7(c) presents the effect of temperature on the extraction of Sn.
sulfides (Sb2S3) 0.04 The leaching rate considerably increases with temperature in the range
Uncertain phase 0.10 55–65 °C. The leaching rate reaches 94.95% at 65 °C and remains un-
Total 9.42
changed at higher temperatures.
Bi Bismuth trioxide (Bi2O3) 14.04 Fig. 7(d) presents the effect of leaching time on the extraction of Sn
Metallic bismuth (Bi) 0.02
from tin anode slime. It is seen that the leaching rate of Sn gradually
sulfides (Bi2S3) 0.04
Total 14.10
increases with leaching duration until it reaches its maximum (about
95%) at 90 min, beyond which it exhibits little variation with time.
Based on the results obtained, a confirmation experiment was con-
hence they can be adsorbed on the surface of SnO2. The CO molecules ducted under the following optimised conditions: Na2CO3/tin anode
then combine with the bridging oxygen to form oxygen vacancies (Eq. slime mass ratio of 1:1, roasting temperature of 1000 °C, roasting time
(6)). These oxygen vacancies are then supplemented by the reactive of 45 min, charcoal powder content of 20%, NaOH concentration of
oxygen anions derived from Na2O, which is a pyrolysis product of 2 mol/L, liquid-to-solid ratio of 14:1, leaching temperature of 65 °C, and
Na2CO3 (Eq. (7)). leaching time of 90 min. The results are given in Table 4. More than
99% of arsenic and more than 95% of Sn are extracted from the tin
O2 + 2e = 2O− (4)
anode slime, while most of the other metals are separated into the
SnO2 + O− = SnO2 ···O− (5) leaching residue. The XRD pattern of the leaching residue shown in
Fig. 1(b) indicates that most of the Sn is leached out, while Sb is con-
SnO2 ···O− + CO = SnO2 + CO2 + e (6)
verted to NaSbO3·3H2O and is concentrated in the residue, which is
SnO2 + Na2 O = Na2 SnO3 (7) beneficial to further recycling. The micromorphological characteristics
of the leaching residue were investigated by SEM-EDS. The results are
Table 3 presents the main metal contents of the different species in
shown in Fig. 8. The large bright white phase (A), which contains
the roasting product under the optimum conditions. It is found that Sn
mainly Bi and O and some Sb, is Bi2O3 with Sb as impurity. The bright
is contained in the roasted sample mainly as Na2SnO3, indicating that
grey phase (B), which is rich in Sb, Bi, and O and has some Cu, is a
most Sn is converted to soluble Na2SnO3 via roasting. It is noteworthy
mixture of Sb2O3 and Bi2O3 with Cu as impurity. In addition, the main
that most of the Sb phases in the anode slime are converted to NaSbO3.
metal contents of the different species in the leaching residue under the
Additionally, it is seen from Table 3 that Bi is mainly in the form of
optimum conditions are presented in Table 5. The results are in ac-
Bi2O3, indicating that the Bi2O3 in the sample did not react during
cordance with those obtained from Fig. 8. By comparing Tables 3 and 5,
roasting. The main chemical reaction of Sb is as follows:
it can be seen that most of the Na2SnO3 contained in the roasted anode
Sb2 O3 + Na2 CO3 + O2 = 2NaSbO3 + CO2 (8) slime is dissolved and separated in the filtrate, implying that the process
of leaching is highly efficient.
3.2. Alkaline leaching of roasted samples
3.3. Sn precipitation from leach solution
As mentioned previously, Sn, Sb, and Bi are present mainly in the
Sn in the leachate exists as Sn (OH )62 −, and its possible precipitation
form of Na2SnO3, NaSbO3, and Bi2O3, respectively. As Na2SnO3 is so-
reaction is depicted in Eq. (11). The effects of CaO/Sn mole ratio,
luble in aqueous solutions but NaSbO3 and Bi2O3 are insoluble, the
precipitation temperature, and precipitation time on the recovery of Sn
roasted anode slime was subjected to water leaching for selectively
were investigated. The filtrate obtained under the optimised conditions
extracting Sn and separating other metals in the residue. The possible
was used for subsequent experiments. The results are shown in Fig. 9.
reaction of Sn during leaching is presented in Eq. (9). Meanwhile, the
hydrolysis reaction of Na2SnO3 likely proceeds as depicted in Eq. (10). CaO + Sn (OH )62 − = CaSnO3 + 2OH− + 2H2 O (11)
Na2 SnO3 (s ) + 3H2 O = Na2 [Sn (OH )6](aq) (9) As can be seen from Fig. 9(a), when the CaO/Sn mole ratio is 1:1,
the recovery rate of Sn is only 28.15%, i.e., the precipitation rate is
SnO32 − + 2H2 O = H2 SnO3 ↓ + 2OH− (10)
29.55%. However, when the mole ratio of CaO/Sn is 3:1, the recovery
The effects of NaOH concentration, leaching temperature, time, and rate of Sn increases significantly and reaches 92.23%, i.e., the pre-
liquid-to-solid ratio on the extraction of Sn were investigated, and the cipitation rate is 97.15%. The maximum precipitation is obtained at the
results are shown in Fig. 7. The initial conditions were fixed as follows: mole ratio of 3.5:1. Under this condition, the recovery rate of Sn is
NaOH concentration of 2 mol/L, leaching temperature of 85 °C, liquid- 94.09%, i.e., the precipitation rate is 99.1%. Considering the chemical
to-solid ratio of 10:1, and leaching time of 120 min. As shown in reagent consumption and recovery rate, 3.5:1 was considered to be the
Fig. 7(a), the leaching rate of Sn is only 63.94% when NaOH con- optimised CaO/Sn mole ratio. Precipitation temperature experiments
centration is 0 mol/L but significantly increases to 88.49% when NaOH were conducted at the optimum CaO/Sn mole ratio of 3.5:1. The results
concentration is raised to 0.5 mol/L. Subsequently, the leaching rate are shown in Fig. 9(b). It can be seen that the recovery and precipitation
gradually increases with NaOH concentration and reaches its maximum rates increase obviously with temperature in the range 15–85 °C, be-
at 2.5 mol/L, beyond which it remains mostly unchanged. As is well yond which they no longer change with temperature. Therefore, 85 °C
known, the increase in NaOH concentration improves the concentration was determined to be the optimised precipitation temperature. Based
of OH− and therefore, prevents the hydrolysis of SnO32 − and improves on the optimised conditions, the recovery and precipitation rates of Sn
the solubility of Na2SnO3 (Gu et al., 2019). Considering the chemical for different process durations were investigated.

6
W. Liu, et al. Minerals Engineering 143 (2019) 105945

Fig. 7. Effects of leaching conditions on the extraction of tin: (a) NaOH concentration, (b) liquid-to-solid ratio, (c) temperature, (d) time.

Table 4 As shown in Fig. 9(c), the recovery rate of Sn increases markedly in

Chemical composition of filtrate and residue. the initial stage and then gradually reaches its maximum at 120 min.
Phases Cu As Sn Sb Pb Bi
With further increase in time, the recovery rate remains mostly un-
changed. When the precipitation time is 120 min, the reaction is almost
Filtrate (g/L) 0.22 0.92 11.05 0.21 0.18 0.23 complete. Hence, 120 min is considered to be the optimised time, and
Residue (%) 3.62 0.016 2.65 23.71 2.04 35.43 the corresponding recovery and precipitation rates of Sn are 93.96%
Leaching rate (%) 24.47 99.65 95.36 5.09 30.25 3.11
and 99.09%, respectively.
Fig. 10 shows the SEM-EDS results and XRD pattern of the pre-
cipitation product. As shown in Fig. 10(a), the growth of crystal grain

Fig. 8. SEM-EDS results of the leaching residue.

7
W. Liu, et al. Minerals Engineering 143 (2019) 105945

1
Table 5 Ahv = C (hv − Eg ) 2 (12)
Main metal content in different species of the leaching residue.
where A , Eg , h , and v represent the absorption coefficient, band gap
Metals Species Content (wt.%)
energy, Planck’s constant, and incident light frequency, respectively,
Sn Cassiterite (SnO2) 0.54 while C denotes a constant. The band gap energy (Eg ) of the samples
sodium stannate (Na2SnO3) 2.45 obtained can therefore be estimated from a plot depicting (Ahv )2 versus
Silicates (SnO2·xSiO2) 0.04
hv . The result shown in Fig. 11 indicates that the bandgap of the
Sulfides (SnS2) 0.06
Total 3.09 CaSnO3 obtained is 4.15 eV. Finally, the overall mass balance for the
flowsheet developed is given in Fig. 12.
Sb Sodium antimonate (NaSbO3) 20.11
Metallic antimony (Sb) 0.29
sulfides (Sb2S3) 0.10 4. Conclusions
Uncertain phase 0.16
Total 20.66
CaSnO3 powder was synthesised from tin anode slime via the pro-
Bi Bismuth trioxide (Bi2O3) 31.30 cess of soda roasting, alkaline leaching, and precipitation. Compared
Metallic bismuth (Bi) 0.02
sulfides (Bi2S3) 0.08
with the traditional preparation of CaSnO3 or treatment of tin anode
Total 31.40 slime, the proposed method uses a process of roast-
ing–leaching–precipitation and secondary Sn resources as raw mate-
rials. The various roasting and leaching process parameters exert dif-
progresses well, and the crystal structure is characterised as the typical ferent effects on the extraction of Sn from the tin anode slime. The
cube-shaped crystal of CaSnO3. Fig. 10(b) and (c) show that the pre- optimum conditions are established as follows: Na2CO3/tin anode slime
cipitated product is highly pure CaSnO3. Based on the above experi- mass ratio of 1:1, roasting temperature of 1000 °C, roasting time of
mental results, the optimised conditions for precipitation are as follows: 45 min, charcoal powder content of 20%, NaOH concentration of
CaO/Sn mole ratio of 3.5:1, temperature of 85 °C, and time of 120 min. 2 mol/L, liquid-to-solid ratio of 14:1, leaching temperature of 65 °C,
Under these conditions, more than 94% of Sn can be recovered in the leaching time of 90 min, CaO/Sn mole ratio of 3.5:1, precipitation
form of CaSnO3. The remaining metals such as Sb and Bi are con- temperature of 85 °C, and reaction time of 120 min. Under these con-
centrated into the leaching residue. ditions, more than 95% of Sn was extracted from the tin anode slime
The energy band structure of a semiconductor plays an important after roasting and leaching, in which Sn was converted into Na2SnO3.
role in determining its photocatalytic activity. The relationship between Furthermore, more than 99% of Sn was precipitated from the leach
absorbance and incident photon energy, hv , can be described using Eq. solution via a process of precipitation with CaO. The XRD and SEM
(12). analyses show that the resulting CaSnO3 is a single phase crystal with
clear edges and corners and its average grain size is lower than 5 μm.

Fig. 9. Effects of precipitation conditions: (a) CaO/Sn mole ratio (85 °C, 120 min), (b) precipitation temperature (3.5:1 CaO/Sn mole ratio, 120 min), (c) precipitation
time (85 °C, 3.5:1 CaO/Sn mole ratio).

8
W. Liu, et al. Minerals Engineering 143 (2019) 105945

Fig. 10. Analysis results of the precipitation product: (a) SEM image, (b) XRD pattern, (c) BSE image, (d) EDS spectrum at point A.

Fig. 11. Band gap energy of the precipitation product.

Additionally, the sample obtained has a cubic perovskite structure,

which renders it suitable for use as a semiconductor material. The
present work provides an economical and eco-friendly method for
producing CaSnO3 from tin anode slime.

Acknowledgements

The authors gratefully acknowledge the financial support by the
National Natural Science Foundation of China (grant number 51804342
and 51874356), the Natural Science Foundation of Hunan Province
(grant number 2019JJ50805), the Innovation Driven Plan of Central
South University (grant number 2015CX005), Key Laboratory of Hunan
Province for Clean and Efficient Utilization of Strategic Calcium-
Fig. 12. Overall mass-balance for the developed flowsheet.
containing Mineral Resources (grant number 2018TP1002), and the
Scientific Research Starting Foundation of Central South University
(grant number 218041).

9
W. Liu, et al.
References
Berbenni, V., Milanese, C., Bruni, G., Girella, A., Marini, A., 2015. Synthesis of calcium
metastannate (CaSnO3) by solid state reactions in mechanically activated mixtures
calcium citrate tetra hydrate [Ca3(C6H5O7)2·4H2O]-tin(II) oxalate (SnC2O4).
Thermochim. Acta 608, 59–64.
Cao, H.Z., Chen, J.Z., Yuan, H.J., Zheng, G.Q., 2010. Preparation of pure SbCl3 from lead
anode slime bearing high antimony and low silver. T. Nonferr. Metal. Soc. 20 (12),
2397–2403.
Fan, C., Song, X., Yu, H., Yin, Z., Xu, H., Cao, G., Zheng, D., Sun, S., 2007. Shape-con-
trolled synthesis of CaSnO3 micro crystals via a precursor route. Mater. Lett. 61 (7),
1588–1591.
Gu, K., Li, W., Han, J., Liu, W., Qin, W., Cai, L., 2019. Arsenic removal from lead-zinc
smelter ash by NaOH-H2O2 leaching. Sep. Purif. Technol. 209, 128–135.
Han, J., Jiao, F., Liu, W., Qin, W., Xu, T., Xue, K., Zhang, T., 2016. Innovative metho-
dology for comprehensive utilization of spent MgO-Cr2O3 bricks: copper flotation.
ACS Sustain. Chem. Eng. 4 (10), 5503–5510.
Han, J., Liang, C., Liu, W., Qin, W., Jiao, F., Li, W., 2017. Pretreatment of tin anode slime
using alkaline pressure oxidative leaching. Sep. Purif. Technol 174, 389–395.
Han, J., Liu, W., Wang, D., Jiao, F., Qin, W., 2015. Selective sulfidation of lead smelter
slag with sulfur. Metall. Mater. Trans. B. 47 (1), 344–354.
Havuz, T., Dönmez, B., Çelik, C., 2010. Optimization of removal of lead from bearing-lead
anode slime. J. Ind. Eng. Chem. 16 (3), 355–358.
Henao, H.M., Masuda, C., Nogita, K., 2015. Metallic tin recovery from wave solder dross.
Int. J. Miner. Process. 137, 98–105.
Huang, Y., Han, G., Liu, J., Chai, W., Wang, W., Yang, S., Su, S., 2016. A stepwise recovery
of metals from hybrid cathodes of spent Li-ion batteries with leaching-flotation-
precipitation process. J. Power. Sour. 325, 555–564.
Junploy, P., Phuruangrat, A., Thongtem, S., Thongtem, T., 2018. Effect of surfactants on
phase, crystal growth and photocatalysis of calcium stannate synthesized by cyclic
microwave and calcination combination. Res. Chem. Intermed. 44 (10), 5981–5993.
Karabulut, Y., Ayvacıklı, M., Canimoglu, A., Guinea, J.G., Kotan, Z., Ekdal, E., Akyuz, O.,
Can, N., 2014. Synthesis and luminescence properties of trivalent rare-earth element-
doped calcium stannate phosphors. Spectrosc. Lett. 47 (8), 630–641.
Kocemba, I., Rynkowski, J.M., 2011. The effect of oxygen adsorption on catalytic activity
of SnO2 in CO oxidation. Catal Today. 169 (1), 192–199.
Li, D., Guo, X., Xu, Z., Tian, Q., Feng, Q., 2015. Leaching behavior of metals from copper
anode slime using an alkali fusion-leaching process. Hydrometallurgy 157, 9–12.
Li, W., Guo, W., Qiu, K., 2013. Vacuum carbothermal reduction for treating tin anode
slime. JOM. 65 (11), 1608–1614.
Liu, B., Zhang, Y., Su, Z., Li, G., Jiang, T., 2017. Formation kinetics of Na2SnO3 from SnO2
and Na2CO3 roasted under CO-CO2 atmosphere. Int. J. Miner. Process. 165, 34–40.
Liu, B., Zhang, Y., Su, Z., Li, G., Jiang, T., 2016a. Function mechanism of CO-CO2 at-
mosphere on the formation of Na2SnO3 from SnO2 and Na2CO3 during the roasting
process. Powder. Technol. 301, 102–109.
Liu, B., Zhang, Y., Su, Z., Li, G., Jiang, T., 2016b. Phase evolution of tin oxides roasted
under CO–CO2 atmospheres in the presence of Na2CO3. Min. Proc. Ext. Met. Rev. 37
(4), 264–273.
Liu, Z., Wang, D., Yang, S., Liu, H., Liu, C., Xie, X., Xu, Z., 2019. Selective recovery of
mercury from high mercury-containing smelting wastes using an iodide solution
system. J. Hazard. Mater. 363, 179–186.
Maul, J., Santos, I.M.G., Sambrano, J.R., Erba, A., 2016. Thermal properties of the
10
Minerals Engineering 143 (2019) 105945
orthorhombic CaSnO3 perovskite under pressure from ab initio quasi-harmonic cal-
culations. Theor. Chem. Acc. 135 (2), 36.
Moshtaghia, S., Ghanbarib, D., Salavati-Niasaria, M., 2015. Characterization of CaSn
(OH)6 and CaSnO3 Nanostructures Synthesized by a New Precursor. J. Nanostruct. 5
(2), 169–174.
Moshtaghi, S., Gholamrezaei, S., Niasari, M.S., 2017. Nano cube of CaSnO3: facile and
green co-precipitation synthesis, characterization and photocatalytic degradation of
dye. J. Mol. Struct. 1134, 511–519.
Mouyane, M., Womes, M., Jumas, J.C., Olivier-Fourcade, J., Lippens, P.E., 2011. Original
electrochemical mechanisms of CaSnO3 and CaSnSiO5 as anode materials for Li-ion
batteries. J. Solid. State. Chem. 184 (11), 2877–2886.
Redfern, S.A., Chen, C.J., Kung, J., Chaix-Pluchery, O., Kreisel, J., Salje, E.K., 2011.
Raman spectroscopy of CaSnO3 at high temperature: a highly quasi-harmonic per-
ovskite. J. Phys. Condens. Matter. 23 (42), 425401.
Rezainik, Y., 2009. Synthesis and processing of SnO2, CaSnO3 and Ca2SnO4 nanopowders
by solid-state reaction technique. Isr. J. Chem. 28 (2), 113–119.
Shi, M., Zhao, H., Zou, J., Yang, B., Li, Y., Wang, Z., Chang, C., Li, W., 2017. Preparation
and characterization of a new long afterglow phosphor CaSnO3: Yb3+. J. Mater. Sci.
Mater. Electron. 28 (14), 10067–10072.
Steinlechner, S., 2018. Characterization and process development for the selective re-
moval of Sn, Sb, and As from anode slime obtained from electrolytic copper refining.
J. Min. Metall. B. 54 (1), 81–89.
Su, Z., Zhang, Y., Han, B., Chen, Y., Lu, M., Peng, Z., Li, G., Jiang, T., 2017a. Interface
reaction between Fe3-xSnxO4 and CaO roasted under CO-CO2 atmosphere. Appl. Surf.
Sci. 423, 1152–1160.
Su, Z., Zhang, Y., Liu, B., Lu, M., Li, G., Jiang, T., 2017b. Extraction and separation of tin
from tin-bearing secondary resources: a review. JOM 69 (11), 2364–2372.
Su, Z., Zhang, Y., Liu, B., Zhou, Y., Jiang, T., Li, G., 2016. Reduction behavior of SnO2 in
the tin-bearing iron concentrates under CO–CO2 atmosphere. Part I: effect of mag-
netite. Powder Technol. 292, 251–259.
Xu, B., Yang, Y., Li, Q., Yin, W., Jiang, T., Li, G., 2016. Thiosulfate leaching of Au, Ag and
Pd from a high Sn, Pb and Sb bearing decopperized anode slime. Hydrometallurgy
164, 278–287.
Zhang, B., Shi, M., Zhang, D., Guo, Y., Chang, C., Song, W., 2017. The comparison:
photoluminescence and afterglow behavior in CaSnO3:Dy3+ and Ca2SnO4:Dy3+
phosphors. J. Mater. Sci. Mater. Electron. 28 (16), 11624–11630.
Zhang, H., Xu, H.B., Zhang, X., Zhang, Y., Zhang, Y., 2014a. Pressure oxidative leaching of
Indian chromite ore in concentrated NaOH solution. Hydrometallurgy 142, 47–55.
Zhang, N., Zhang, Z.C., Zhou, J.G., 2011. Synthesis of CaSnO3 nanofibers by electro-
spinning combined with sol–gel. J. Sol-Gel. Sci. Technol. 58 (2), 355–359.
Zhang, Y., Han, B., Su, Z., Liu, B., Jiang, T., 2018. Formation characteristics of calcium
stannate from SnO2 and CaCO3 synthesized in CO-CO2 and air atmospheres. J. Phys.
Chem. Solids. 121, 304–311.
Zhang, Y., Liu, B., Su, Z., Chen, J., Li, G., Jiang, T., 2016. Effect of Na2CO3 on the pre-
paration of metallic tin from cassiterite roasted under strong reductive atmosphere. J.
Min. Metal. B 52 (1), 9–15.
Zhang, Y., Su, Z., Liu, B., You, Z., Yang, G., Li, G., Jiang, T., 2014b. Sodium stannate
preparation from stannic oxide by a novel soda roasting-leaching process.
Hydrometallurgy 146, 82–88.
Zhao, H., Shi, M., Zou, J., Yang, B., Li, Y., Wang, Z., Chang, C., 2017. Synthesis and
luminescent properties of a new cyan afterglow phosphor CaSnO3: Gd3+. Ceram. Int.
43 (2), 2750–2755.