Resources, Conservation & Recycling 164 (2021) 105195

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Resources, Conservation & Recycling

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Eco-friendly and efficient extraction of valuable elements from copper anode T

mud using an integrated pyro-hydrometallurgical process
Bin Xua, Yanzhu Chena, Zhonglin Donga, , Tao Jianga, Bangsheng Zhangb, Guiqing Liub,
⁎

Junkui Yangc, Qian Lia, Yongbin Yanga

a
School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, China
b
Jiangsu BGRIMM Metal Recycling Science & Technology Co. Ltd, Xuzhou, Jiangsu, China
c
Qinghai Copper Industry Co., Ltd., Xining, Qinghai, China

ARTICLE INFO ABSTRACT

Keywords: An integrated pyro-hydrometallurgical process was developed to extract valuable elements from copper anode
Anode mud mud, a hazardous solid waste. Sulfation roasting-water adsorption was first conducted to recover selenium.
Comprehensive extraction Then, water leaching-iron powder cementation was adopted to extract copper from the roasted residue.
Pyro-hydrometallurgical process Afterwards, selective chloride leaching-H2C2O4 reduction was employed to extract gold in the copper-leaching
Cleaner production
residue. Last, sulfite leaching-Na2S2O4 reduction was used to recover silver from the gold-leaching residue, and
Thermodynamic analysis
the barren leachate could be circularly used for silver leaching with the addition of a small quantity of lixiviant.
Lead was hardly dissolved during the above treatments and a lead concentrate was finally obtained. 97.0% of
selenium, 91.9% of copper, 98.7% of gold, 98.6% of silver and 99.8% of lead in the mud were recovered by this
integrated pyro-hydrometallurgical process, and the grades of obtained crude selenium, sponge copper, metallic
gold, metallic silver and lead concentrate products reached 93.6%, 86.4%, 99.5%, 96.3% and 52.5%, respec-
tively. This integrated process possesses the advantages of improved environmental friendliness, high recovery
rates of valuable elements and low energy consumption and reagent dosage, and thus has a bright prospect in
industrial application.

1. Introduction
Copper anode mud is an important industrial by-product generated
at the bottom of an electro-refining tank during copper electrolytic
refining, which makes up 0.2%−0.8% of anode copper (Hait et al.,
2002). It is regarded as a hazardous solid waste because of the en-
richment of toxic and harmful components. However, it is also an im-
portant raw material for extracting valuable elements such as gold,
silver, selenium, copper and lead (Chen et al., 2015; Li et al., 2018).
Currently, pyro-metallurgical Kaldo process is the predominant method
to extract these elements, which is generally comprised of water
washing, pressure acid leaching, reductive smelting, oxidative blowing
and refining, and electrolytic refining (Hait et al., 2009). The purpose of
the first and second steps is to pre-remove copper for eliminating/
weakening its negative effect on subsequent processes. The third and
fourth steps are performed in a Kaldo furnace with the aim of further
removing impurities and forming a gold-silver alloy. Selenium and lead
are separately recovered from the fume and slag (He et al., 2018). The
Kaldo process for gold and silver recovery is mature in developed
countries, and the Kaldo furnace is environmentally friendly and has a
high treatment capacity (usually over 3000 tons per year). Thus, it has
been adopted by many large smelters (Jian and Xie., 2014). Never-
theless, its initial investment is high and high energy consumption is
needed because the required temperature is high. In addition, a large
proportion of copper smelters in China are small and medium smelters,
where anode mud yield (about 1000 tons per year) is generally lower
than the treatment capacity of Kaldo furnace, and thus the furnace
cannot be fully utilized. More importantly, at present the Kaldo process
needs to be imported into China, which is associated with a high cost.
So, the Kaldo process is generally not adopted by these small and
medium smelters (Lu and Xu., 2016).
For many small and medium smelters in China, reductive smelting
and oxidative blowing and refining are implemented with other types of
furnaces such as side blowing furnace and converter instead of Kaldo

Corresponding author: Zhonglin Dong, Peace Building, School of Minerals Processing & Bioengineering, Central South University, 410083, Changsha, Hunan,
⁎

P.R. China.
E-mail addresses: xubincsu@csu.edu.cn (B. Xu), 1397022205@qq.com (Y. Chen), dongzhonglincsu@csu.edu.cn (Z. Dong), jiangtao@csu.edu.cn (T. Jiang),
zbsvictory@163.com (B. Zhang), Charles_liu32@163.com (G. Liu), 369177646@qq.com (J. Yang), csuliqian@126.com (Q. Li), ybyangcsu@126.com (Y. Yang).

https://doi.org/10.1016/j.resconrec.2020.105195
Received 9 July 2020; Received in revised form 28 September 2020; Accepted 30 September 2020
Available online 06 October 2020
0921-3449/ © 2020 Elsevier B.V. All rights reserved.
B. Xu, et al.
Fig. 1. (a) appearance and (b) XRD spectrogram of anode mud samples.
furnace (Tu et al., 2011). Likewise, the alternative method is also ap-
plied by other smelters in the world such as Outokumpu pori smelter in
Finland. However, the three high-temperature procedures are per-
formed in two different furnaces. So, compared with the Kaldo process
where the three procedures are finished in one furnace, this pyro-me-
tallurgical process in China presents the disadvantages of more complex
processes, longer production periods and higher energy consumptions
(Xu et al., 2016a). This promoted the development of hydro-
metallurgical process for extracting gold and silver from copper anode
mud in China because its initial investment and energy consumption
are generally lower due to its relatively simple equipment and low
operation temperature (Xu et al., 2017; Yang et al., 2019).
At present, thiosulfate leaching, thiourea leaching and chloride
leaching are the three main hydrometallurgical methods studied to
extract gold from copper anode mud (Dong et al., 2017). However, both
thiosulfate and thiourea are unstable and easily oxidized by the used
oxidants of cupric and ferric ions in their pulps, therefore resulting in
high reagent consumptions (Dong et al., 2019; Xu et al., 2016b;
Yu et al., 2015). Furthermore, the two processes are susceptible to other
elements such as lead and arsenic, and their presences can cause gold
leaching passivation, thus leading to low leaching rates (Ranjbar et al.,
2014; Yavuz and Ziyadanogullari., 2000). As for conventional chloride
leaching which generally uses the solution containing HCl and oxi-
dizing agent such as NaClO3, Ca(ClO)2, Cl2, H2O2 or HNO3, the selective
leaching of gold is also difficult (Ding et al., 2017; Xing and Lee., 2017).
During subsequent gold recovery from leachate, the dissolved metals
may be precipitated and enter gold product, leading to the decrease of
product purity.
For silver extraction from anode mud, ammonia leaching, nitric acid
leaching and sulfite leaching have been the most widely studied in the
past few decades. Silver can be efficiently extracted by ammonia
leaching, but high concentration of ammonia is generally implemented
and its volatilization can readily deteriorate the working environment
(Hyk and Kitka., 2017). Moreover, poisonous hydrazine hydrate is
commonly used to recover the dissolved silver from the leachate
(Xiao et al., 2018). Nitric acid is also an efficient silver leaching agent.
However, large amounts of impurity elements especially for lead can be
readily dissolved, and their co-precipitations with silver in subsequent
recovery procedure make it difficult to obtain a high-grade silver pro-
duct. Furthermore, poisonous NO gas will be generated (Khaleghi et al.,
2014). In comparison, sulfite is clean and has a good selectivity for
silver leaching, and hence it is a more appropriate reagent. However, it
can be easily oxidized by oxygen dissolved in the pulp, and thus high
sulfite consumption is inevitable and high concentration of sulfite is
generally employed to get a high silver leaching rate (Valiuniene et al.,
2010). In addition, the formaldehyde that has been widely utilized for
silver recovery is also highly toxic.
2
Resources, Conservation & Recycling 164 (2021) 105195
Hydrometallurgical process is also developed to extract these va-
luable elements where selenium and copper are hydrometallurgically
pre-extracted before gold and silver extraction. However, when the pre-
extraction is performed under atmospheric condition, it is difficult to
obtain high leaching rates (Kilic et al., 2013). Moreover, the two ele-
ments will be dissolved synchronously, leading to the difficulty of their
complete separation from the leachate (Xiao et al., 2019). Pressure
acid/alkaline leaching can enhance copper and selenium leaching rates.
Nevertheless, their simultaneous dissolutions are also inevitable and
subsequent separation is problematic (Liu et al., 2014). In addition,
high equipment cost and operating requirement are needed for pressure
leaching (Li et al., 2017). Utilizing the dramatic difference of volatili-
zation temperature between selenium and copper, pyro-metallurgical
recovery of selenium followed by hydrometallurgical extraction of
copper may be a feasible countermeasure to solve the above problems.
In this study, an integrated pyro-hydrometallurgical process was put
forward to extract gold, silver, selenium, copper and lead from a copper
anode mud. First, Sulfation roasting-water adsorption and water
leaching-iron powder cementation was successively used to recover
selenium and copper. Then, chloride leaching followed by H2C2O4 re-
duction was employed to selectively recover gold from copper-leaching
residue. At last, Na2SO3 leaching in a closed reactor followed by
Na2S2O4 reduction was adopted to efficiently recover silver from gold-
leaching residue. Lead was gradually enriched and remained in the final
residue. This integrated process can cleanly comprehensively recover
the main valuable elements from the hazardous solid waste of copper
anode mud, and has significant meaning for the development of cleaner
production and circular economy in China and other countries.
2. Experimental work
2.1. Material and reagents
The copper anode mud produced from copper electrolytic refinery
of a medium-scale copper smelter in western China was used as raw
material in this study. As shown in Fig. 1(a), the mud particles
stuck together to form clumps because it contained plenty of water. So,
it was placed into the oven at 100 °C for two days. The dried sample was
ground using a ball mill to the sizes of 90% less than 0.074 mm for
subsequent detections and experiments.
The results of chemical compositions analysis presented in Table 1
shows that the mud contains 0.16% Au, 5.36% Ag, 4.52% Se, 11.68%
Cu and 28.65% Pb, and the economic value of the five elements ac-
counts for 98.5% of the total economic value of the mud, and thus the
goal of this study is to recover them. The mud also contains 2.38% As
that is the major harmful element. XRD spectrogram displayed in
Fig. 1(b) indicates that PbSO4 and CuSO4 are separately the primary
B. Xu, et al. Resources, Conservation & Recycling 164 (2021) 105195

Table 1 with an electric agitator and the reaction temperature was controlled by
Chemical compositions of the copper anode mud (wt.%). an electro-thermostatic water bath. The detailed experiment procedure
Element Au Ag Se Cu Pb O has been stated in our previous work (Xu et al., 2019a). For each re-
covery experiment for leached metal, 50 mL of the leachate was first
Content 0.16 5.36 4.52 11.68 28.65 24.00 introduced into the reactor which was heated to a preset temperature.
Then, a certain amount of reductant was added, and the stirrer was
S Bi Sb As Ba Ni Sn
turned on. At the end of the experiment, the solution was filtered, and
10.38 3.86 2.32 2.38 2.11 1.36 1.21 solid precipitate and filtrate were obtained. The recovery rate of each
element was calculated based on its concentration variation before and
after reduction, and the obtained reduction product was dried for
lead and copper phases in the mud, and selenium exists as Ag2Se and subsequent detections.
Cu2Se phases, which is accordance with the previous report that sele-
nium is generally associated with copper and silver in copper anode
mud (Khanlarianan et al., 2019). Silver occurs in the form of Ag2Se 2.3. Analytical methods
phase. Gold phase was not detected because its content was relatively
low compared with the above elements. The reagents employed were The contents/concentrations of concerned elements in solid/solu-
analytical pure and ultrapure water was utilized in all the experiments. tion were analyzed by an inductively coupled plasma optical emission
spectroscopy (ICP-OES, PS-6, Baird), and acid digestion was required
before the analysis of solid sample. Mineralogical compositions of the
2.2. Experimental methods sample were determined by an X-ray diffractometer (XRD, D8 Advance,
Bruker AXS). The obtained products were characterized by scanning
The flowchart of the integrated pyro-hydrometallurgical process is electron microscope coupled with energy dispersive spectrometer
shown in Fig. 2. The experiments include three aspects, i.e. sulfation (SEM-EDS, MIA3, TESCAN). The methods of constructing Eh-pH dia-
roasting, leaching and recovery. Sulfation roasting experiment was gram and species distribution diagram were illustrated in our previous
conducted in a horizontal tube furnace mainly including a horizontal study (Xu et al., 2019b).
quartz tube and an electric furnace, as displayed in Fig. 3. The roasting
temperature was monitored by a Pt-Rh thermocouple located in the 3. Results and discussion
center of the furnace and regulated by a digital temperature controller
with an accuracy of ± 1 °C. The produced deleterious off-gasses such as 3.1. Selenium extraction
SO2 and As2O3 were absorbed with calcium hydroxide solution. Prior to
roasting, sulfuric acid and anode mud were sufficiently mixed and the 3.1.1. Thermodynamic analysis
furnace was heated to a predetermined temperature. At the beginning Sulfation roasting-water adsorption was first performed to recover
of the experiment, the porcelain boat loaded with a proper amount of selenium, and the relevant reactions are shown in Eqs. (1)-(4). Selenium
anode mud mixed with sulfuric acid was pushed into the middle of in Ag2Se and Cu2Se phases was volatilized as SeO2 gas while silver and
quartz tube. Then, air pump was started to blow the air, and the copper were converted into Ag2SO4 and CuSO4. Meanwhile, SO2 was
roasting experiment was performed in air atmosphere. At the end of the generated in the fume. SeO2 was easily adsorbed by water to form
roasting, the power supply was cut off and the quartz tube was cooled, H2SeO3 that was then reduced by SO2 gas into elemental selenium.
and the roasted residue was collected for further analyses and leaching The changes of Gibbs free energy (ΔG) of Eqs. (1)-(4) as a function
tests. of temperature were calculated by HSC Chemistry 6.0 software, and the
All leaching tests were performed in a 250 mL PVC reactor equipped results are displayed in Fig. 4. The ΔG of Eqs. (1)-(2) are negative values

Fig. 2. The proposed pyro-hydrometallurgical process for extracting gold, silver, selenium, copper and lead from copper anode mud.

3
B. Xu, et al.
Fig. 3. Schematic diagram of experimental equipment for sulfation roasting.
Fig. 4. ΔG-T diagrams of Eqs. (1)-(4).
in the temperature range studied, indicating that the two reactions can
occur spontaneously. In comparison, the ΔG of Eq. (2) is smaller, and
thus the Cu2Se oxidation reaction is more likely to happen in terms of
thermodynamics. The reactions (3) and (4) are performed below
100 °C, and their ΔG are negative under the temperature conditions.
Thus, the reactions of SeO2 adsorption and H2SeO3 reduction are also
spontaneous.
Ag2Se + 2H2SO4 + O2 = Ag2SO4 + SeO2 + SO2 + 2H2O (1)
Cu2Se + 3H2SO4 + 3/2O2 = 2CuSO4 + SeO2 + SO2 + 3H2O (2)
SeO2 + H2O = H2SeO3 (3)
H2SeO3 + 2SO2 + H2O = Se + 2H2SO4 (4)
3.1.2. Sulfation roasting-water adsorption
The results of effects of roasting conditions on selenium volatiliza-
tion are indicated in Fig. 5(a–c). Copper in the mud can be transformed
into soluble sulfate through sulfation roasting. So, we also considered
the effects of roasting conditions on copper leaching from the roasted
residue, which was conducted at NaCl 6.7 g/L, temperature 60 °C, li-
quid-solid weight ratio 5:1, and time 30 min. Sodium chloride was
added to prevent silver leaching together with copper through gen-
erating silver chloride precipitate.
As shown in Fig. 5(a), selenium volatilization rate reached 98.5% at
acid/mud weight ratio 0.6:1, and nearly all of the selenium in the mud
was volatilized. However, copper leaching rate was only 79.6%, which
4
Resources, Conservation & Recycling 164 (2021) 105195
was due to the low sulfation degree of copper phases at a low ratio (i.e.
a low sulfuric acid dosage). The extent of selenium volatilization rate
slowly increased with the increase of the ratio. In comparison, copper
leaching rate increased as the ratio raised from 0.6:1 to 1:1. After that,
it first kept steady and then began to drop when the ratio was beyond
1.4:1. At an excessively high acid/mud ratio, the most of sulfuric acid
was not consumed during roasting and remained in the residue, which
led to a high acid concentration for subsequent copper leaching. The
dissolution of impurity elements especially for arsenic would evidently
increase in this case, which might promote the generation of cupric
arsenate precipitate on copper surface (Xu et al., 2020). As a result of
this, the copper surfaces became passivated, leading to the decrease of
its leaching rate.
As presented in Fig. 5(b), at 300 °C selenium volatilization and
copper leaching rates were only 89.3% and 79.5%, respectively. Both
these recovery numbers increased with the increase of temperature up
to 500 °C. Further increase of temperature did not evidently promote
selenium volatilization and copper leaching. Particularly, copper
leaching rate declined dramatically when the temperature was over
600 °C. This is probably because that at an excessively high tempera-
ture, copper sulfate could decompose into copper oxysulfate and/or
copper oxide Tumen and Bailey., 1990), as displayed in Eqs. (5)-((6).
The two decomposition products have lower solubility in water com-
pared with copper sulfate, thereby resulting in the low copper leaching
rate (Ozer et al., 2017).
As given in Fig. 5(c), 74.3% of the selenium was volatilized and
65.8% of the copper was leached when the mud was roasted for 10 min.
Increasing roasting time effectively promoted selenium volatilization
and copper leaching, and selenium volatilization rate of 99.7% and
copper leaching rate of 89.2% were obtained after roasting for 60 min.
With further extension of time, the volatilization and leaching rates
basically remained unchanged.
From the above, the optimal sulfation roasting conditions are acid/
mud weight ratio 1:1, temperature 500 °C and time 60 min. The ap-
pearance of crude selenium product shown in Fig. 6(a) indicated that it
was very fine black powder. The XRD spectrogram displayed in
Fig. 6(b) demonstrated that elemental selenium was obtained. SEM
image shown in Fig. 6(c) manifested that the nearly globular particles
were stacked together. Acid digestion followed by ICP-OES analysis was
used to determine the chemical composition of selenium product, and
the result indicated that selenium purity was as high as 93.6%. The
major impurities in the product were sulfur and arsenic whose contents
were separately 3.6% and 2.4%.
From the above, selenium was completely volatilized after sulfation
roasting, and the volatilized selenium could be efficiently adsorbed by
water and subsequently reduced by SO2 gas originating from the
B. Xu, et al.
Fig. 5. Effects of reaction conditions on selenium volatilization and copper leaching. (a) effect of acid/ mud ratio under the conditions: temperature 400 °C and time
60 min; (b) effect of roasting temperature under the conditions: acid/mud ratio 1:1 and time 60 min; (c) effect of roasting time under the conditions: acid/mud ratio
1:1 and temperature 500 °C.
oxidation of sulfides in the mud. As a result, a high-grade crude sele-
nium product was obtained.
2CuSO4 = CuO•CuSO4 + SO2 + 1/2O2
CuO•CuSO4 = 2CuO + SO2 + 1/2O2
3.2. Copper extraction
After selenium extraction, a roasted residue was obtained and its
appearance and XRD spectrogram are shown in Fig. 7(a–b). The residue
surface was faded yellow, and Ag2Se and Cu2Se phases in anode mud
disappeared while Ag2SO4 phase was formed after the roasting, in-
dicating that selenium was completely volatilized, and silver phase was
efficiently sulfated through sulfation roasting. According to the XRD
spectrogram in Fig. 7(b), the main copper phase in the roasted residue
is copper sulfate. So, water leaching was adopted to extract copper, and
its optimal conditions ascertained by conditional tests were NaCl 6.7 g/
L, liquid-solid weight ratio 5:1, temperature 80 °C and time 60 min, and
92.3% of the copper was leached under the conditions.
The leached copper was recovered from the leachate using iron
powder cementation performed at Fe/Cu molar ratio 1.4:1, temperature
40 °C and time 20 min, and 99.6% of the dissolved copper was pre-
cipitated. Fig. 8(a) displayed the appearance of obtained sponge copper
product, and it was comprised of some flake-like solid blocks. XRD
Resources, Conservation & Recycling 164 (2021) 105195
spectrogram (Fig. 8(b)) manifested that metallic copper was the main
phase of sponge copper. Cuprous oxide phase was also detected, which
was due to the partial oxidation of newly generated metallic copper by
(5)
dissolved oxygen during the cementation process. SEM image
(6) (Fig. 8(c)) indicated that the microstructure of spongy copper is porous,
and there were some flaky particles aggregating and clustering to-
gether. The chemical composition of copper product was determined by
ICP-OES analysis, and the result showed that the product purity
achieved 86.4%. The major impurities in the product were bismuth,
iron, sulfur and arsenic whose contents were 2.1%, 1.6%, 0.9% and
0.3%, respectively. Therefore, a sponge copper with relatively high
grade was obtained through iron powder cementation.
3.3. Gold extraction
3.3.1. Thermodynamic analysis
Gold in the copper-leaching residue existed as elemental gold and
was extracted by chloride leaching. The Eh-pH diagrams of Au–H2O
system and Au–Cl–H2O system were plotted, and are separately pre-
sented in Fig. 9(a-b). As shown in Fig. 9(a), gold exists in the form of
elemental gold in the whole stable region of water, and Au3+ ion only
appears at the high potentials that are beyond the upper limit of this
stable region. Also, the pH range of Au3+stable region is relatively
narrow. Hence, it is very difficult to leach gold in the residue with
common oxidants in the absence of coordination agent.
5
B. Xu, et al. Resources, Conservation & Recycling 164 (2021) 105195

Fig. 6. (a) appearance, (b) XRD spectrogram and (c) SEM image of crude selenium product.

For the Au–Cl–H2O system (Fig. 9(b)), gold(Ⅲ) can stably exist as
AuCl4− complexes in the shaded area in aqueous solution with the
presence of chloride. Compared with the situation of Au–H2O system,
the oxidation potential of gold is significantly reduced and the pH range
of gold(Ⅲ) stable region is evidently increased for the Au–Cl–H2O
system. Thus, the oxidation of elemental gold to soluble gold(Ⅲ) is
much easier in the Au–Cl–H2O system. From the above, it can be
concluded that the complexing reaction between Au3+and Cl− ob-
viously reduces the difficulty of dissolving elemental gold in the copper-
leaching residue.
3.3.2. Gold leaching test
The XRD spectrogram of Au, Ag and Pb-rich residue is shown in
Fig. 10(a). After copper and selenium extractions, their phases

Fig. 7. (a) appearance and (b) XRD spectrogram of the roasted residue.

6
B. Xu, et al. Resources, Conservation & Recycling 164 (2021) 105195

Fig. 8. (a) appearance, (b) XRD spectrogram and (c) SEM image of sponge copper product.

disappeared and silver phase was transformed into AgCl. The solution
containing H2SO4, NaClO3 and NaCl was used for gold leaching from
the copper-leaching residue, and the relevant reaction was displayed in
Eq. (7). One of the advantages of selecting NaCl and H2SO4 as leaching
reagents is that they can impede the dissolutions of silver and lead
through the formation of AgCl and PbSO4 precipitates. The effects of
NaClO3 concentration on gold, silver and lead leaching were studied
under the conditions of NaCl 8.5 g/L, H2SO4 150 g/L, liquid-
solid weight ratio 5:1, time 4 h and temperature 70 °C, and the results
are shown in Fig. 10(b).
As indicated, 73.2% of gold in the residue was leached with 7.9 g/L
NaClO3, and the low leaching rate can be ascribed to the incomplete
oxidation of gold because of the low oxidant dosage. The gold dis-
solution markedly increased with the increase of NaClO3 concentration

Fig. 9. Eh-pH diagrams of (a) Au–H2O and (b) Au–Cl–H2O systems at [Au]=10−3 M and [Cl]=1 M.

7
B. Xu, et al.
Fig. 10. (a) XRD spectrogram of Au, Ag and Pb-rich residue; (b) Effect of NaClO3 concentration on gold, silver and lead leaching.
in the range of 7.9–30.5 g/L, and gold leaching rate of 99.1% was
achieved at 30.5 g/L NaClO3. Afterwards, the leaching rate remained
stable. In comparison, silver and lead leaching rates were closed to 0%
in the whole concentration range. From the above, selective gold
leaching from the copper-leaching residue with negligible dissolutions
of silver and lead could be realized with the H2SO4eNaClO3eNaCl
solution. This will be favorable to gold recovery from the leachate and
recycle of the barren leachate, owing to the little interference of un-
desirable cations.
2Au + ClO3− + 6H+ + 7Cl− = 2AuCl4− + 3H2O
3.3.3. Gold recovery test
After chloride leaching, the dissolved gold was recovered from the
leachate by oxalic acid (H2C2O4) reduction, and the reaction is shown
in Eqs. (8)-(9). H2C2O4 was selected as the reductant since it has strong
reduction ability (E0= – 0.481 V vs SHE). Also, it is a clean reagent
because its oxidation reaction product is nontoxic CO2 gas. H2C2O4 is a
weak acid which can be dissociated into HC2O4– and C2O42–, as de-
scribed in Eqs. (10)-(11). The fractions of H2C2O4, HC2O4– and C2O42–
as a function of pH are displayed in Fig. 11. When pH was below 1.2,
H2C2O4 was the main species. HC2O4– became the primary species in
the pH rang of 1.2–4.2. After that, C2O42–turned to be the predominant
Fig. 11. Speciation distribution diagram of H2C2O4eH2O system at different pH
values.
Resources, Conservation & Recycling 164 (2021) 105195
species. The gold reduction experiment was carried out under the op-
timum conditions of temperature 70 °C, pH 1.5, H2C2O4 dosage 9.7 g/L
and time 150 min, which were obtained by conditional tests. 99.6% of
the dissolved gold was recovered as metallic gold product under the
conditions.
Fig. 12(a) showed the appearance of the product, and the obtained
lamellar precipitate was gold. SEM image Fig. 12(b)) indicated that
some thin and transparent flaky particles closely aggregated together.
Two evident gold peaks occurred in the EDS spectrum of product
(Fig. 12(c)). The result of ICP-OES analysis for the product indicated
(7)
that gold purity reached 99.5%, and the remaining components were
mainly copper and lead compounds, which might be due to the for-
mation of a little cupric oxalate (CuC2O4) and lead oxalate (PbC2O4)
precipitates during the reduction. Silver was not detected in the gold
product. According to the result of chemical composition analysis of
chloride leachate, the concentrations of Cu2+, Pb2+ and Ag+ were
separately 9.1 × 10−3, 1.4 × 10−4, 2.4 × 10−6 mol/L. Based on
Eqs. (10)-((12), the C2O42− concentration can be displayed as Eq. (13).
Taking the values of Ka1 5.9 × 10−2, Ka2 6.4 × 10−5, pH 1.5,
[H2C2O4]Total 9.7 g/L into this equation, the C2O42− concentration was
calculated to be 1.4 × 10−4 mol/L. So, the ion products of [Cu2+]
[C2O42−], [Pb2+][C2O42−] and [Ag+]2 [C2O42−] were separately
1.3 × 10−6, 2.0 × 10−8 and 8 × 10−16. The solubility products (Ksp)
of CuC2O4, PbC2O4 and Ag2C2O4 were 4.4 × 10−10, 4.8 × 10−10 and
5.4 × 10−12, respectively (Xiong et al., 2014). The ion products of
[Cu2+][C2O42−] and [Pb2+][C2O42−] were larger than the solubility
products of CuC2O4 and PbC2O4, and thus Cu2+ and Pb2+ could react
with C2O42- to generate CuC2O4 and PbC2O4 precipitates and entered
the gold product. The ion product of [Ag+]2[C2O42−] was smaller than
the solubility product of Ag2C2O4, and hence Ag+did not precipitate.
From the above, the method of H2C2O4 reduction could be used to
effectively recover gold from the chloride leachate and a high-grade
metallic gold product was obtained by this method.
2HAuCl4 + 3H2C2O4 = 2Au↓+ 8HCl + 6CO2↑ (8)
2HAuCl4 + 3HC2O4− = 2Au↓+ 6CO2↑+ 5H +
+ 8Cl −
(9)
+
H2C2O4 ⇌ H + HC2O4− Ka1=[H +
][HC2O4−]/[H2C2O4] (10)
HC2O4−⇌ H +
+ C2O42− +
Ka2=[H ][C2O4 2−
]/[HC2O4−] (11)
[C2O42−] =[H2C2O4]Total – [HC2O4−] – [H2C2O4] (12)
[C2O42−] +
= [H2C2O4]Total/(1+([H ]/Ka2) + ([H ] /Ka1Ka2)) + 2
(13)
8
B. Xu, et al.
Fig. 12. (a) appearance, (b) SEM image and (c) EDS spectrum of metallic gold product.
3.4. Silver extraction
3.4.1. Thermodynamic analysis
After gold extraction, silver existed in the form of AgCl in the gold-
leaching residue. AgCl can coordinate with SO32− to form silver sulfite
complexes, as displayed in Eq. (14). The coordination number is
dependent on SO32- concentration and solution pH (Xiao et al., 2018).
The variations of silver species at different Na2SO3 concentration and
pH are investigated by constructing the silver speciation distribution
diagram, and the results are shown in Fig. 13(a-b).
As indicated in Fig. 13(a), AgCl is gradually dissolved and converted
into silver sulfite complexes with the increase of SO32- concentration.
When SO32- concentration is lower than 0.15 mol/L, AgSO3− is the
complex having the highest fraction in solution. Ag(SO3)23− becomes
the dominant species when SO32- concentration is in the range of
0.15–0.85 mol/L. When SO32- concentration is beyond this range, Ag
(SO3)35− possesses the highest fraction.
As presented in Fig. 13(b), only AgCl occurs when pH is lower than
4.5, which is because SO32- can not exist under the acid condition and
thus the coordination reactions between AgCl and SO32- do not happen.
After this pH, the fraction of AgCl decreases quickly and those of Ag
(SO3)23−and Ag(SO3)35− gradually increase, indicating that AgCl is
transformed into silver sulfite complexes. Based on the above analysis,
Na2SO3, an environmentally friendly and efficient complexant, was
used to leach the silver from the gold-leaching residue.
AgCl + xSO32- = Ag(SO3)x(2x-1)- + Cl− (x = 1, 2, 3) (14)
9
Resources, Conservation & Recycling 164 (2021) 105195
3.4.2. Silver leaching test
The XRD spectrogram of Ag and Pb-rich residue is displayed in
Fig. 14(a). After chloride leaching of gold, PbSO4 and AgCl were the
main phases in the residue. According to our previous study (Xu et al.,
2016b), sulfite could be easily oxidized by the oxygen dissolved in the
solution, which caused excessive leaching reagent consumption. In
order to solve this problem, closed reactors were adopted. The effect of
Na2SO3 concentration on silver leaching in open and closed reactors
was investigated at temperature 35 °C, pH 10 and time 6 h, and the
result is shown in Fig. 14(b).
In an open reactor, only 14.5% of the silver in the gold-leaching
residue was leached at 50 g/L Na2SO3. Increasing Na2SO3 concentration
in the range of 50–250 g/L evidently facilitated silver leaching and the
maximum leaching rate of 92.5% was obtained at 250 g/L Na2SO3. The
increase of leaching reagent concentration promoted the coordination
reactions between AgCl and SO32−, which could account for the in-
crease of leaching rate. However, as Na2SO3 concentration increased to
300 g/L, silver leaching rate dropped to 84.2%. The likely reason is that
under the condition of high concentration of Na2SO3, more SO32- was
oxidized by dissolved oxygen into SO42− that could readily react with
Ag+to form Ag2SO4 precipitate.
In a closed reactor, 51.5% of the silver could be dissolved at 50 g/L
Na2SO3, which was evidently higher than 18.5% obtained at the same
concentration in an open reactor. 99.2% of the silver was leached with
150 g/L Na2SO3, and after that the leaching rates basically kept steady.
This showed that 150 g/L Na2SO3 was sufficient for the silver leaching
from the gold-leaching residue. In comparison with the results gained
B. Xu, et al.
Fig. 13. Effects of (a) Na2SO3 concentration and (b) pH on silver species fraction for AgCl–SO32−–H2O system under the conditions of (a) [Ag] 0.15 M, [Cl] 0.15 M
and pH 10; (b) [Ag] 0.15 M, [Cl] 0.15 M and [SO32−] 1.2 M.
Fig. 14. (a) XRD spectrogram of Ag and Pb-rich residue; (b) effect of Na2SO3 concentration on silver leaching with closed and open reactors at temperature 35 °C, pH
10 and time 6 h.
with an open reactor, higher silver leaching rates could be got with
lower sodium sulfite dosage in the closed reactor due to the avoidance
of lixiviant oxidation by dissolved oxygen. Thus, using the closed re-
actor for sulfite leaching of silver is an effective measure to reduce the
leaching reagent consumption.
3.4.3. Silver recovery
The dissolved silver in the leachate was recovered by a nontoxic
reductant of sodium hydrosulfite (Na2S2O4, E0= – 1.12 V vs SHE). As
indicated in Eq. (15), silver sulfite complexes are reduced to metallic
silver, and the reductant itself is oxidized into sulfite that is the leaching
reagent for silver in this study. Hence, after silver recovery, if the barren
leachate is reused for silver leaching, the sodium sulfite dosage will be
reduced. The silver reduction was performed under the optimal con-
ditions of temperature 25 °C, pH 10, Na2S2O4 16 g/L and time 20 min,
which were also established by conditional experiments. 99.4% of the
silver in the leachate was recovered as metallic silver product under the
conditions.
Fig. 15(a) showed the appearance of product which was dark gray
powder. XRD spectrogram (Fig. 15(b)) manifested that silver was the
10
Resources, Conservation & Recycling 164 (2021) 105195
only phase. SEM image (Fig. 15(c)) indicated that flaky round particles
with different grain sizes superimposed on each other and there were
many interspaces between the particles. The result of ICP-OES analysis
revealed that silver purity reached 96.3%.
Cyclic sulfite leaching of silver from fresh gold-leaching residue in
the closed reactor was conducted to investigate cycle performance of
the barren leachate. The effects of supplementary Na2SO3 dosage and
cycle number on silver leaching were studied where operating para-
meters were consistent with those in Section 3.4.2, and the results are
shown in Fig. 16(a-b). As indicated in Fig. 16(a), 85.8% of the silver in
the residue was dissolved by the barren leachate without adding new
Na2SO3. Silver leaching rates obviously raised with the addition in-
creased of Na2SO3 in the range of 0–30 g/L, and it reached 98.9% at
30 g/L Na2SO3. Thus, the addition of new Na2SO3 evidently improved
silver leaching. After that, the increase of leaching rates turned to be
slight. Thus, the optimum supplementary dosage of Na2SO3 was 30 g/L.
Fig. 16(b) showed the effect of cycle number on silver leaching where
30 g/L Na2SO3 was added in each cycle. The result showed that silver
leaching rate only decreased from 98.9% to 96.2% after 5-time cycles,
and the slight decline might be due to the accumulation of impurity
B. Xu, et al. Resources, Conservation & Recycling 164 (2021) 105195

Fig. 15. (a) appearance, (b) XRD spectrogram and (c) SEM image of metallic silver product.

ions in the barren leachate. This indicated that the barren leachate
could be cyclically used for silver leaching from gold-leaching residue.
For each cycle, we found that when the leaching was finished, the
pulp pH value slightly increased from initial 10 to 10.3. This can be
ascribed to the augmented OH−concentration originating from the
gradual hydrolysis of SO32- during leaching, as shown in Eq. (16). On
the contrary, the pH value of barren solution dropped to 9.8 after silver
reduction, which is due to the consumption of OH− in the solution
during reduction procedure, as presented in Eq. (15). After replenishing
sodium sulfite, the pH of barren solution was adjusted to 10 for silver

Fig. 16. Effects of (a) supplementary Na2SO3 dosage and (b) cycle number on silver leaching from fresh gold-leaching residue with barren leachate in a closed
reactor.

11
B. Xu, et al.
Fig. 17. Distributions of concerned elements in each leachate and residue. “–” means that the element was non-detectable because of its extremely low concentration.
leaching. The pH of barren solution during its cycle use changed in
cycles.
From the above, silver could be effectively recovered from the sul-
fite leachate through Na2S2O4 reduction and a high-grade metallic
silver product was attained. Furthermore, when the barren leachate was
circularly used, where only 20% of initial lixiviant dosage was added in
each cycle, a high silver leaching rate still could be obtained after 5-
time cycles. Thus, the barren leachate has a good cycle performance.
S2O42- + 2Ag(SO3)x(2x-1)- + 4OH− = 2Ag↓+ 2(x + 1)SO32- + 2H2O
(15)
SO32− + H2O= HSO3− + OH−
3.5. Elemental distribution analysis
Fig. 17 presented the distribution of selenium, copper, gold, silver,
lead and arsenic in the obtained leachate and residue from each stage of
the developed pyro-hydrometallurgical process.
99.7% of selenium in the anode mud was volatilized during sulfa-
tion roasting. 97.3% of the volatilized selenium was adsorbed by water
and then reduced by generated SO2 gas in the fume, and the remaining
2.4% entered the gypsum residue deriving from the adsorption of SO2
by calcium hydroxide solution. Thus, 97.0% of selenium in the mud was
converted into the crude selenium product.
There was no copper volatilization during roasting and it remained
in the roasted residue. 92.3% of copper in the residue was dissolved
Resources, Conservation & Recycling 164 (2021) 105195
during water leaching and 99.6% of the leached copper was replaced by
iron powder. Thus, 91.9% of copper in the mud entered the sponge
copper product. 7.2% of copper was extracted during gold leaching and
nearly all the leached copper was left in the barren leachate after gold
recovery. The rest of copper in the mud mainly remained in the final
residue (i.e. lead concentrate).
Gold was very stable during sulfation roasting and water leaching,
and it was enriched in the copper-leaching residue. 99.1% of gold in the
residue was dissolved during chloride leaching, and 99.6% of the dis-
solved gold was reduced by H2C2O4. Therefore, 98.7% of gold in the
mud went into the metallic gold product. The remaining gold entered
(16) the lead concentrate.
Silver was steady during sulfation roasting and hardly dissolved
during copper and gold leaching, and it was enriched in the gold-
leaching residue. 99.2% of silver was leached by sulfite leaching in a
closed reactor, and 99.4% of the dissolved silver was recovered by
Na2S2O4 reduction. So, 98.6% of silver in the mud entered the metallic
silver product. The rest of the silver went into the lead concentrate.
Lead was inert during the extractions of selenium, copper, gold and
silver and gradually enriched in lead concentrate. 99.8% of lead entered
the concentrate whose grade reached 52.5%.
By contrast with the above five valuable elements, the harmful
element arsenic presented a relatively dispersive distribution. 15.7% of
arsenic in the mud was volatilized during sulfation roasting, and 30.6%
and 69.4% of the volatilized arsenic (i.e. 4.8% and 10.9% of the total
arsenic) deported to the crude selenium and gypsum residue. 60.2% of
the arsenic was dissolved during copper leaching. After copper
12
B. Xu, et al.
Table 2
Chemical compositions and acidities of barren solutions obtained after the recovery of copper, gold and silver (mg/L).
Barren solution Cu Se Ag Au Pb
Copper 82.9 9.5 0.36 – 15.8
Gold 2068.4 5.4 0.18 1.5 28.3
Silver 22.3 5.3 95.1 – 68.6
recovery, 8.6% of the arsenic entered the sponge copper product, and
the remaining 51.6% was kept in the copper-containing barren lea-
chate. 15.6% and 0.3% of the arsenic were separately dissolved during
chloride leaching and sulfite leaching, and they remained in corre-
sponding barren leachates after gold and silver recoveries. The re-
maining 8.2% of arsenic entered the lead concentrate.
According to the developed pyro-hydrometallurgical process flow-
chart displayed in Fig. 2, after recovering copper, gold and silver, three
kinds of barren leachates were produced and their chemical composi-
tions and acidities are shown in Table 2. It can be expected that the
concentrations of impurity components in these barren leachates will
increase with the increase of cycle time, which may exert unfavorable
influences on copper, gold and silver leaching. In order to solve this
problem, after recycling for certain times, a certain proportion of the
solution can be termly pumped out, and then is treated by the tech-
nologies of sulfide precipitation, neutralization precipitation, mem-
brane separation, etc. After the purification treatment, the accumulated
impurity components are effectively removed and the purified solutions
can be returned to the leaching stage.
The arsenic concentrations in copper and gold barren leachates se-
parately reached 2326.8 and 916.3 mg/L, and thus they need to be
properly treated. For the arsenic in copper barren leachate, the in-
troduced iron ions during iron powder cementation can be fully utilized
to precipitate arsenic as stable scorodite compound (Shibayama et al.,
2010). After arsenic precipitation, the remaining iron is recovered as
iron hydroxide product. Similarly, the arsenic in gold barren leachate
can be recovered in the form of copper arsenate by the precipitation
reaction between arsenate anions and cupric cations deriving from the
dissolution of remaining copper in water leaching residue during
chloride leaching of gold (Chen et al., 2001). Thus, arsenic in the two
barren leachates can be removed effectively without the addition of
extra reagent.
4. Conclusions
In this study, an integrated pyro-hydrometallurgical process has
been developed to recover gold, silver, selenium, copper and lead from
a copper anode mud. 99.7% of selenium in the mud was volatilized
through sulfation roasting, and 97.3% of the volatilized selenium was
adsorbed by water and reduced into crude selenium by SO2 in the fume.
92.3% of copper in the roasted residue was leached with water, and
99.6% of the leached copper was precipitated by iron powder ce-
mentation. 99.1% of gold in the copper-leaching residue was selectively
dissolved by the solution containing H2SO4, NaClO3 and NaCl, and
99.6% of the dissolved gold was recovered by H2C2O4 reduction. 99.2%
of silver in the gold-leaching residue was leached with Na2SO3 in a
closed reactor, and 99.4% of the leached silver was reduced into me-
tallic silver by a green reagent of Na2S2O4. The barren leachate that
contained abundant SO32− deriving from Na2S2O4 oxidation showed a
good recycle performance, and a silver leaching rate of 96.2% could be
got after its five-time circularly used where only 20% of initial lixiviant
dosage was added in each cycle. The elemental distribution analysis for
the integrated pyro-hydrometallurgical process showed that 97.0% of
selenium, 91.9% of copper, 98.7% of gold, 98.6% of silver and 99.8% of
lead in the copper anode mud separately entered their separate pro-
ducts (i.e. crude selenium, sponge copper, metallic gold, metallic silver
and lead concentrate), and their grades reached 93.6%, 86.4%, 99.5%,
13
Resources, Conservation & Recycling 164 (2021) 105195
As Fe Bi Sb Ba pH
2326.8 24,986.5 76.4 125.3 236.4 0.6
916.3 22.3 236.4 98.4 42.5 1.5
14.9 12.6 6.8 7.6 3.4 9.8
96.3% and 52.5%, respectively. The pyro-hydrometallurgical process
can cleanly and efficiently recover the main valuable elements from the
mud with low reagent dosage, and thus has an extensive application
prospect in metallurgical industry.
CRediT authorship contribution statement
Bin Xu: Conceptualization, Writing - original draft, Funding ac-
quisition, Resources, Validation. Yanzhu Chen: Investigation, Formal
analysis, Writing - review & editing. Zhonglin Dong:
Conceptualization, Investigation, Formal analysis, Validation, Data
curation. Tao Jiang: Conceptualization, Supervision, Writing - review
& editing. Bangsheng Zhang: Investigation, Formal analysis. Guiqing
Liu: Investigation, Formal analysis. Junkui Yang: Investigation,
Formal analysis. Qian Li: Supervision, Writing - review & editing.
Yongbin Yang: Supervision, Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors are thankful for the financial support from National
Natural Science Foundation of China (No. 51504293), Qinghai
Provincial Major Scientific and Technological Special Project of China
(No. 2018-GX-A7), Hunan Provincial Natural Science Foundation of
China (No. 2018JJ4038), National Key Research and Development
Program of China (No. 2018YFC1902006) and Fundamental Research
Funds for the Central Universities of Central South University (No.
150110003).
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