Hydrometallurgy 197 (2020) 105460

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Recovery of scattered and precious metals from copper anode slime by T

hydrometallurgy: A review
Gongqi Liua,b,1, Yufeng Wua,b,1, Aijun Tangc, De'an Pana,b, , Bin Lia,b
⁎

a
College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, PR China
b
Institute of Circular Economy, Beijing University of Technology, Beijing 100124, PR China
c
China Association of Electronics Equipment for Technology Development, Beijing 100037, PR China

ARTICLE INFO ABSTRACT

Keywords: Scattered and precious metals (SPMs: Se, Te, Au, Ag, Pt, and Pd) play an irreplaceable role in advanced methods
Copper anode slime and materials, and their global consumption has been growing in recent decades. However, SPM consumption
Scattered and precious metals and recycling are very unbalanced, resulting in a shortage of supply and some uncertain risk regarding their
Hydrometallurgical method sustainability. Copper anode slime (CAS) is an important component of secondary resources, and it contains a
Separation
large amount of SPMs. Because of the complicated occurrence state of SPMs, the technique of extracting and
Extraction
separating them from CAS is quite different from that of raw ore. This paper focuses on the distribution of
minerals and current non-cyanide hydrometallurgical methods for extracting Se, Te, Au, Ag, Pt, and Pd from
CAS. In particular, in terms of recovery technology, some representative methods, including selective separation,
extraction, precipitation, and reduction of hydrometallurgical method, as well as the recovery process, chemical
reaction formulas, and the optimization and recycling situations of SPMs are reviewed, and the recycling po-
tential, value, and supply risks of CAS are elaborated. Although these methods have achieved quite satisfactory
results in recovering certain SPMs from CAS, it is undeniable that these still face challenges for further pro-
motion. In addition, from the perspective of economic assessment of recovery potential, supply sustainability,
and technical improvement, future strategies for recovering SPMs from CAS are proposed. This paper is intended
to serve as a guide for the future development research on CAS, and provides detailed information on the
promotion of SPMs recycling.

1. Introduction
Globally, the demand for scattered and precious metals [SPMs,
specifically gold (Au), silver (Ag), platinum (Pt), palladium (Pd), sele-
nium (Se), and tellurium (Te)) is growing faster than the demand for
other base metals, which is mainly attributed to rapid developments in
semiconductors (Luo et al., 2017), printed circuit boards (Jeong, 2013),
catalysts (Wei et al., 2019), photovoltaic (Max and Armin, 2012), and
new functional materials. Although the use of SPMs is generally low
relative to other metal resources, the growth rate of these advanced
materials can pose a significantly risk to the supply SPMs (Damien
et al., 2020).
The mineral resources containing SPMs are of many types and
variable grade, resulting in high mining and utilization costs (Işıldar
et al., 2017; Rana et al., 2020). Further, > 99% of these resource exist
in only a few countries, such as South Africa and Canada (Zhang et al.,
2017a). As a result, most countries are extremely short of SPMs and face
serious supply risk (Ding et al., 2020). Moreover, excessive and illegal
mining of raw minerals, primitive mining technology, and inadequate
supporting policies, particularly in developing countries, inevitably
increase the environmental and supply risks of SPMs (Eygen et al.,
2016; Sverdrup et al., 2014a; Sverdrup et al., 2014b; Wang et al.,
2019). Thus, the recovery of secondary resources, such as waste printed
circuit boards, spent catalysts, tailings, and other metallurgical wastes,
make up for the shortage of SPMs to a certain extent (Diaz et al., 2016;
Li et al., 2018). Exploitation and sustainable use of the SPMs in these
secondary resources is crucial to the sustainable development of mining
resources.(Sverdrup and Vala, 2016).
However, the recycling of SPMs from secondary resources still faces
some challenges, especially for recycling methods (Damien et al., 2020;
Zhang and Xu, 2018). Traditional high-energy–consumption pyr-
ometallurgy and high-toxicity and high-pollution cyanide leaching

⁎
Corresponding author at: College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, PR China.
E-mail address: pandean@bjut.edu.cn (D. Pan).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.hydromet.2020.105460
Received 9 May 2020; Received in revised form 13 August 2020; Accepted 19 August 2020
Available online 21 August 2020
0304-386X/ © 2020 Published by Elsevier B.V.
G. Liu, et al.
methods have gradually been abandoned. In the meantime, because of
the low grade and complexity of secondary resources, the recovery and
utilization of SPMs are becoming increasingly difficult. However, hy-
drometallurgy, because of its broader selection of reagents, economy at
smaller scales (pyrometallurgical smelters normally need large feed-
stocks), ability to handle/process low grade and high grade raw ma-
terials, and lower recycling costs and energy consumption, has devel-
oped rapidly in the field of SPM recycling (Jeon et al., 2020). In this
paper, the hydrometallurgical method of recovering Au, Ag, Pt, Pd, Se,
and Te is reviewed with copper anode slime (CAS) as an example.
At present, more than 80% of the world's copper is obtained by
electrolytic refining, which inevitably produces a large amount of CAS
(Arroyo-Torralvo et al., 2017). As a by-product of copper electrolytic
refining, CAS contains a large number of SPMs, and thus, has become an
important part of secondary resources (Ding et al., 2017; Wang et al.,
2017; Yıldırım et al., 2014).
Only a few of these SPMs exist in elemental form; most of them form
complex compounds, such as intermetallics and alloys, with base metals
such as Cu (Melo et al., 2016; Ling et al., 2010), which are summarized
in Section 2. Because of the addition of copper sludge, copper cables,
waste printed circuit boards, and other types of recycled copper to the
copper smelting process, the anode slime is rich in tin (Sn), manganese
(Mn), arsenic (As), lead (Pb), and other heavy metals, causes the
composition of anode slime to fluctuate greatly (Li et al., 2020;
Markovic et al., 2013; Yu et al., 2018; Zhang et al., 2018).
In recent years, with the recycling of resources and the significant
attention to environmental issues, the extraction of valuable elements
from CAS, especially SPMs, has been widely studied by many scholars
(Cooper, 1990; Ranjbar et al., 2017; Toraiwa and Abe, 2000; Wei and
Man, 2017). At present, the research on CAS mainly focuses on the
separation of valuable elements by hydrometallurgy, especially the
recovery of precious metals (Liu et al., 2020; Yang et al., 1997). The
selection of CAS treatment process is affected by the content and
morphology of the main elements, the production scale, and the
smelting process of each copper electrolytic plant (Hait et al., 2009).
There are currently four broad categories of processes for recovering
valuable elements from CAS (Melo et al., 2016; Cooper, 1990; Hait
et al., 2009): pyrometallurgy, partial hydrometallurgy, surface che-
mical (e.g. flotation) and physical separation processes, and hydro-
metallurical processes. The general process is shown in Fig. 1, and in-
volves the following steps: (1) pretreatment of Cu separation; (2)
separation and recovery of Te and Se; (3) extraction of Au and Ag; (4)
recovery of the remaining non-ferrous heavy metals and platinum
group metals (PGMs, especially Pt and Pd) from the intermediate
Fig. 1. The general hydrometallurgical recovery process of CAS.
2
Hydrometallurgy 197 (2020) 105460
products (Amer, 2003; Hait et al., 2009).
Thus far, although several experts and scholars have conducted
extensive research on the recovery of valuable metals from CAS by
hydrometallurgy, the systematic classification and summary of the ex-
traction and separation methods of SPMs in CAS remain largely un-
explored (Cooper, 1990). Therefore, based on the study of the mineral
composition characteristics of the main elements of CAS, the recovery
principle and methods of typical SPMs from CAS were analyzed in this
study, and are presented in detail. The recycling potential, value, and
supply risks, as well as the supply trend and recovery potential of CAS
were evaluated. The purpose of this study was to review the compre-
hensive recovery and treatment of SPMs present in CAS so as to provide
guidance for the future development and research on CAS for sustain-
able recovery of these elements. In the review, emphasis is placed on
methods that are perceived to do less harm to human beings, animals
and the environment.
2. Composition and characteristics of primary metals in CAS
CAS, a by-product of the electrolytic refining of Cu (including pri-
mary copper and regenerated copper), is a mixture of various sub-
stances that are poorly soluble in the electrolyte during the electrolytic
refining of copper anodes (Fahidy, 2006; Gu et al., 1995; Petkova,
1997). A typical production process of CAS is shown in Fig. 2 (Bard and
Sobral, 2008). The composition of CAS and its contents vary from
smelter to smelter; the composition mainly depends on the mineral raw
materials, copper anode composition, casting quality, and technical
conditions of electrolysis (Chen et al., 2015). Through a literature re-
view of studies conducted across the globe, we summarized the con-
tents of CAS elements and the occurrence of each element in different
smelters. In general, the yield of primary CAS is 0.2–1.0% of refined
copper. It is dark gray in color and has a grain size of approximately
75–150 μm (Hait et al., 2009). As shown in Table 1, most CAS contain
precious metals: Au, Ag, Pt, Pd, and scattered metals: Se and Te, as well
as toxic and harmful elements such as Pb, As, Sb, Bi, Fe, Sn, Ni, Cu, and
other elements (Chen and Dutrizac, 1991, 2005; Wei and Man, 2017).
By comparison, it was found that the content of Cu in decopper anode
slime was significantly lower than that in primary CAS, whereas the
contents of precious metals were higher.
The raw materials of copper smelting enterprises are complex and
changeable; these include electroplating sludge, copper-containing
sludge, surface treatment waste, and waste printed circuit boards
among others, and thus large amounts of Sn (19–45%), As (4–13%), Cu
(5–10%), and Pb (7–17%) are introduced into the CAS, the contents of
G. Liu, et al. Hydrometallurgy 197 (2020) 105460

which vary greatly (Markovic et al., 2013). As shown in Fig. 3(a)

(Nassar et al., 2015), high amounts of Se, Te, Au, Ag, Pt, and Pd and
small amounts of Pb, As, Ni, and Zn occur in association with copper,
which the reason for the complex composition of CAS (Nassar et al.,
2015). The mineralogical characterization of typical CAS is shown in
Fig. 3(b).
According to the literature review, we summarized the mineral
forms of the main elements in CAS and the results are presented in
Table 2 (Amer, 2003; Yavuz and Ziyadanoğullari, 2000). It was found
that the elements in the anode slime were mainly divided into the
following categories:

(1) Metals having negative electronegativity such as Zn, Fe, Ni, Sn, Pb,
Cr, etc., are first dissolved in the divalent ion state into the elec-
trolyte during copper electrolysis without being precipitated on the
cathode (Liu et al., 2019). Most of these elements are strongly
oxidized in the smelting process, leading to their presence mainly in
the form of corresponding oxides (Kiviluoma et al., 2016). Some
amphoteric oxides, such as those of Pb and Sn, easily form hydro-
lyzed sulfates during electrolysis, producing insoluble alkali salts
and entering the anode slime.
(2) The second type of impurities are metals such as Ag, Au, Pt, and Pd,
which are more positive than copper (Hait et al., 2009). These
impurities do not dissolve during copper electrolysis, but sink to the
bottom of the cell in a very fine dispersed state. Among them, Au,
Pt, and Pd exist in free form, and most of the Ag exists in the form of
selenide, telluride, sulfide, and chloride. Only trace amounts of Ag
Fig. 2. A typical production process of copper anode slime (Bard and Sobral, are dissolved in the copper electrolyte to form silver sulfate during
2008). copper electrolysis. The Ag combines with the chloride ions in the
electrolyte to form silver chloride, which is transferred to the anode

Table 1
Composition of CAS in different refineries, wt, %.
Material Refineries Au Ag Pt* Pd* Cu Ni As Te Se Sb Pb Bi Sn References

a Toyama, Japan 0.4237 7.92 18 90 26.67 / / 2.08 13.25 / 9.44 / / (Sanuki et al., 2007)
a Toyama, Japan 1.04 17 20 200 0.23 / 0.41 0.93 11.2 1.73 35.1 / / (Sanuki et al., 2007)
a Changsha, china 0.13 9.68 / / 13.33 2.57 4.13 0.95 4.05 3.4 13.23 / / (Liu et al., 2014)
a Alexandria, Egypt / 0.46 / / 18.57 0.94 0.94 / / 1.3 15.3 / 9.8 (Amer, 2003)
a Shenyang, China 0.21 9.94 / / 16.35 1.67 4.6 1.69 8.08 4.46 13.74 / / (Yang et al., 2013)
a Jiangxi, China 0.353 8.75 / / 11.63 / 4.13 2.58 5.26 4.69 7.24 / / (He et al., 2014)
a Yuannan, China 0.37 22.25 / / 17.81 0.97 6.8 3.17 8.9 8.52 18.56 2.55 0.81 (Wang et al., 2017)
a Shenyang, China 0.016 2.62 27.6 95.5 11.68 45.78 0.77 0.5 3.93 / / / / (Lu et al., 2015)
a Jinchuan Group Ltd., China 0.31 8.38 / / 13.06 / / / 3.4 / 13.25 / / (Li et al., 2017b)
a Sarkusan, Turkey 0.23 2.8 / / 25.8 0.29 3.93 0.9 4.68 0.99 12.93 0.15 8.1 (Kilic et al., 2013)
a Daye Nonferrous Metal, China 0.21 10.45 300 / 11.91 / 4.1 0.58 5.22 5.09 16.16 / 1.01 (Li et al., 2015a)
a Er-balir copper plant, Turkey 0.002 0.22 / / 23.1 0.82 / 0.008 0.041 0.24 15.42 0.11 0.24 (Rüşen and Topçu, 2017)
a Tehran, Iran 0.08 7.07 / / 7.0 0.03 0.42 / 13.66 0.1 4.42 0.08 / (Khanlarian et al., 2019)
a Jiangxi, China 0.208 4.81 / / 18.36 / 0.64 / 10 / 5.94 / / (Xiao et al., 2018)
a CCR, Noranda 0.18 19.5 / / 18.7 0.67 1.14 1.2 10 1.68 8 0.77 / (Cooper, 1990)
a Beijing, China 0.12 3.03 / / 26.57 / / / / 4.30 5.28 / 4.30 (Wang et al., 2014)
a Changsha, China 0.32 16.85 / / 16.02 0.69 / 1.30 0.15 12.62 10.72 1.76 / (Li et al., 2016)
a ER&S, Australia 0.1 9 / 900 13 2 1.2 0.2 5.8 3 31 0.3 5 (Cooper, 1990)
a IMI, UK 0.07 5.5 40 80 14 9 3.5 0.6 2 3.5 22 0.5 5 (Cooper, 1990)
a Inco 0.12 6.37 / / 21 17 0.5 1.8 8.4 0.09 1.7 0.14 / (Cooper, 1990)
a Kidd Creek 0.15 12.7 / / 26 0.03 0.45 0.05 19.5 0.09 22 0.28 / (Cooper, 1990)
a Palabora 0.33 7.8 500 700 53.4 4.5 0.15 2.2 3.6 / / 0.01 / (Cooper, 1990)
a Phelps Dodge, El Paso 0.12 12.2 7 60 27.1 0.64 1.7 3.1 8.8 0.66 4.65 / / (Cooper, 1990)
a Rabak, Turkey 0.11 4.8 5 20 24.7 0.05 2.3 3 7.9 / / 0.5 / (Cooper, 1990)
a Sakuysan, Turkey 0.1 4.73 / / 26.7 0.82 3.6 2.5 7.6 1.3 1.7 / / (Cooper, 1990)
a Southwire, Georgia 0.02 4.1 800 3500 10 8.4 1.4 / 0.6 9.4 13.1 0.5 5.3 (Cooper, 1990)
a Chilean, refinery 0.1 0.32 / / 17.1 / 3.4 / / 0.49 2.6 / / (Melo et al., 2016)
b Changsha, china 0.011 0.442 / 95.3 0.93 1.52 0.22 / / 7.24 10.59 / 46.2 (Xu et al., 2016a)
b Southern of China 0.099 2.22 / / / / / / / 10.81 19.52 / 26.55 (Ding et al., 2017)
b Mhangura, Zimbabwe 1.0 62 500 100 2 0.3 0.16 1 10 0.07 1.8 0.13 0.15 (Cooper, 1990)
b Yunnan, China 0.003 0.17 / / 0.21 / / 3.42 0.41 15.39 28.24 3.9 / (Zha et al., 2019)
b Yunnan, China 0.007 0.35 / / 0.37 / / 3.82 0.22 25.43 49.70 7.94 / (Zha et al., 2019)
b Jinchuan Group Ltd., China 0.55 14.81 / / 2.43 / / / 6.1 / 23.31 / / (Li et al., 2017b)
b Chilean refinery 0.23 0.49 / / 0.97 / 0.92 / / 1.1 1.1 / / (Melo et al., 2016)
b Erzurum, Turkey 0.13 2.05 / / 0.33 / 0.93 / / 17.16 29 / 15.95 (Tokkan et al., 2012)

a: primary CAS; b: decopperized anode slime; *: ppm; “/”: means no data available.

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G. Liu, et al. Hydrometallurgy 197 (2020) 105460

Fig. 3. (a) The wheel of metal companionality (Nassar et al., 2015); (b) Mineralogy characterization of typical CAS.
Source: Guangdong Research Institute of Rare-Metal.

Table 2 3. Extraction and separation methods of Se and Te

The phase composition of CAS.
Elements Mineral composition Se and Te are chalcogenide (VI A) elements that are widely used in
the medical, chemical, electronics, ceramics, metallurgy, and glass
Ag Ag2SO4/ Ag2Se/ Ag2Te/ CuAgSe/ AgCl/ (Ag/Au)Te2/ Ag2S/ Ag2O manufacturing industries (Manuel et al., 2018; Spinks et al., 2016).
Cu Cu2S/ Cu2Se/ Cu2Te/ Cu2O/ CuAgSe/ Cu2SO4/ Cu2Cl They also play an important role in the fields of cutting-edge method,
Te Ag2Te/ Cu2Te/ (Ag/Au)Te2/ Te
Se Ag2Se/ Cu2Se/ CuAgSe/ Se
national defense, and the high-tech industry. Indeed, they are known as
As As2O3/ BiAsO4/ SbAsO4 the “vitamins of modern industry, national defense and cutting-edge
Sn Sn(OH)2SO4/ SnO2 method” (Chaudhary et al., 2016; Lu et al., 2015; Wang, 2011). Anode
Au Au/ (Ag/Au)Te2 slime is the main source of raw materials for Se and Te (Zhang and Xu,
Bi Bi2O3/ BiAsO4
2018). About 90% of Se and Te are derived from anode slime produced
Sb Sb2O3/ SbAsO4
Pb PbSO4/ PbSb2O6 by electrolytic refining in copper and lead refineries (Li et al., 2017b).
Fe Fe2O3 The forms of Se and Te in CAS are Ag2(Te, Se), Cu2(Te, Se), and (Au,
Si SiO2 Ag)Te2, which are difficult to dissolve in non-oxidizing acid or alkali
PGMs Pt/ Pd solutions (Chen and Dutrizac, 2014; Xie et al., 2010). Based on the
Ni NiO
Zn ZnO
physical and chemical properties of Se and Te in CAS, a series of ex-
traction and separation methods have been developed, as shown in
Fig. 4.
slime.
(3) In CAS, Se and Te exist in the form of compounds such as Ag2(Se,
3.1. Extraction of Se and Te
Te), Cu2(Se, Te), and (Ag, Au)Te, and these compounds sink into
the anode slime without electrolysis (Feng and Taskinen, 2013;
The extraction of Se and Te in CAS has been extensively studied by
Makuei and Senanayake, 2018) because the Group IB elements (Cu,
researchers (Dutton et al., 1971; Swinbourne et al., 1998). The recovery
Ag, Au) have a special affinity with Group VIA elements (O, S, Se,
of these elements is mainly carried out during the recovery of precious
Te), causing selenium and tellurium to be the main carriers of Au
metals such as Au and Ag, and it is often accompanied by the Cu re-
and Ag (Shao et al., 2020). Therefore, the recovery of precious
moval (Kilic et al., 2013). The main recovery methods of Se and Te from
metal Au and Ag from CAS and the recovery of Se and Te are in-
solutions and residues include sulfation roasting, alkali leaching, soda
separable.
smelting, and other methods (Amer, 2003; Bezuidenhout et al., 2013;
(4) Another group of impurities are metals with potentials similar to
Hait et al., 2002; Hait et al., 2009; Xie et al., 2010). Table 3 summarizes
that of Cu, such as Sb, As, and Bi (Chen et al., 2017). In the copper
some advanced recovery methods, process conditions, process char-
electrolysis process, trivalent metal sulfate is easily formed and then
acteristics and recovery rates of Se and Te (Makuei and Senanayake,
hydrolyzed to form an insoluble hydroxide. It is then deposited as a
2018; Yang et al., 2018).
compound form (As2O3, Sb2O3, Bi2O3) in the anode slime (Wang
Sulfuric roasting is the method most often used for the recovery of
et al., 2011).
Se and Te from CAS among some enterprises (Khanlarian et al., 2019).
Se, Te, and Cu are converted into corresponding oxides or sulfates by
It can thus be seen that the phase composition of CAS is very
using oxygen in the air as oxidant at 300–700 °C (Hyvärinen et al.,
complex. Therefore, the recovery method of CAS should be selected
1989). The main characteristic of this method is that the volatilized
based on the physical and chemical properties and existing forms of
SeO2 (at 335 °C) can be directly reduced by SO2 in an aqueous solution,
various elements to extract SPMs.
whereas telluride in the calcined sand is directly leached with an acidic
solution. However, this method is not suitable for treating CAS con-
taining large amounts of selenium (Hyvärinen et al., 1989).
To avoid SO2 contamination, selenium in CAS can also be recovered

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G. Liu, et al. Hydrometallurgy 197 (2020) 105460

Fig. 4. Hydrometallurgical method for recovery of Se and Te from CAS.

Table 3
Recovery of Se and Te from CAS.
Leaching systems Reagents Recycling procedures Target element References
and yield

Alkaline leaching NaOH 4 M NaOH, O2: 2 L/min, 90 °C, 180 min, liquid/solid ratio: 10:1. 86% Se (Kilic et al., 2013)
Acid leaching HNO3 + H2SO4 560-mL: 0.5 M HNO3 + 1.25 M H2SO4, 90 °C, 160 min, stirring speed: 98.3% Se (Li et al., 2017b)
300 rpm.
Acid leaching HNO3 + H2SO4 Gas pressure: 0.1 MPa, 388 K, solid-liquid ratio of 0.2 g /mL, 2 mol/L 99.23% Se (Li et al., 2017a)
H2SO4, 0.07 mol/L HNO3, 2 h.
Acid leaching+ H2SO4 + H2O2 Microwave power: 450 W, reaction time: 5 min, solid/liquid ratio: 95.97% Te (Yang et al., 2015)
Microwave-assisted 0.10 g/mL, 1.5 mol/L H2SO4, 0.8 mol/L H2O2, stirring speed: 500 r/ 95.37% Se
min.
alkaline pressure oxidative NaOH 2.0 mol/L NaOH, 200 °C, oxygen partial pressure: 0.7 MPa, 3 h, 99.0% Se (Liu et al., 2014)
leaching liquid/solid ratio: 5:1, stirring speed: 750 rpm.
Acid leaching HNO3 90 °C, 4 M HNO3, 60 min. 99.0% Se (Abdollahy and Shafaei,
2004)
Soda roasting+ Na2CO3+ NaOH+H2SO4 Roasting: Na2CO3/copper anode slime: 0.1, 500 °C, 0.5 h; 97% Se (Lu et al., 2015)
Alkaline leaching+ Alkaline leaching: 20 g/L NaOH, 80 °C, 1.0 h; 99.9% Te
Acid leaching Acid leaching: 90 g/L H2SO4 70 °C, 1.0 h.
Sulfation roasting+ H2SO4 300–600 °C. as oxidants to convert Se, Te and Cu into corresponding 96% Se (Hait et al., 2009).
Acid leaching oxides or sulfates. 96% Te
Chlorination leaching NaCl+H2SO4 60 °C, 150 min, NaClO3 65 g/L, NaCl 50 g/L, H2SO4 300 g/L, liquid/ 96.5% Se (Zhang et al., 2014a)
solid ratio: 4:1. 76.4% Te
Acid leaching H2SO4 + MnO2 1.2 g MnO2, 1.0 M H2SO4 600 rpm, 80 °C,6 h, 100% Se (Xiao et al., 2019)
Alkali fusion+ NaOH +NaNO3 Fusion: NaOH/NaNO3/slime mass ratio: 6:1:3, 600 °C, 45 min; 97% Se (Dong et al., 2015)
Water leaching Leaching: solid/water ratio: 60 g/L, 60 °C, 30 min.

5
G. Liu, et al.
by oxidative roasting (Hoffmann, 1989). At 700–800 °C, 95% of Se is
oxidized to SeO2, which can be absorbed by an alkaline solution to
obtain the corresponding selenite. During the roasting process, no loss
of Ag occurs and no SO2 gas is generated.
Another method of converting Se and Te is to mix sodium carbonate
(Na2CO3) or sodium bicarbonate (NaHCO3) with CAS in a certain pro-
portion and roast it at 350–500 °C (Hoffmann, 1989). Lu et al. (2015)
reported that in the soda roasting process, Cu in the form of Cu4SeTe in
CAS was oxidized to CuO, whereas Se and Te were converted into
Ag2SeO4 and Cu3TeO6, respectively. In the alkaline leaching process,
Ag2SeO4 was easily dissolved and leached, but Cu3TeO6 was still dif-
ficult to leach. Therefore, in the roasting-leaching process, Se was
preferentially leached, whereas good leaching of the Cu3TeO6 re-
maining in the alkali leaching slag was obtained by using dilute sulfuric
acid. Under optimal experimental conditions, the recovery rates of Se,
Te, and Cu were 97%, 100% and 96%, respectively. The roasting
temperature and the amount of sodium carbonate added are the key
factors, and high-temperature-resistant equipment is needed. This
method is suitable for treating CAS that contains low amounts of Se and
Te.
Leaching of elements in CAS can also carried out using sulfuric acid
under conditions of high temperature and high pressure (Cooper,
1990). The high-pressure leaching environment strengthens the kinetic
conditions of the reaction, causing most tellurides to oxidize and enter
the solution in the form of sulfates and tellurites. Then, only some of the
selenide enters the solution in the oxidation reaction, with most of it
remains in the residue because the redox potential of Se is higher than
that of other metals. In order to solve the problem of the low leaching
rate of selenium in an acid system, Liu et al. (2014) studied the leaching
process of alkaline pressure oxidation of CAS. Under the optimal con-
ditions—NaOH concentration 2.0 mol/L, oxygen pressure 0.7 MPa,
time 3.0 h, temperature 200 °C, and liquid/solid ratio 5:1—the Se
leaching rate reached more than 99%. This method is suitable for
treating CAS with high Se content. However, the disadvantage of this
method is that the consumption of oxygen is too large and the cost of
equipment and maintenance is too high.
Chlorine gas can be used as a strong oxidizer to convert Se and Te in
CAS into water-soluble selenite and tellurite acid (Yang et al., 2015).
When excess chlorine is introduced during the reaction, Se and its
compounds are oxidized to form H2SeO4. The advantage of this method
is that the Se recovery rate is high. However, under the conditions of a
strong oxidizing agent and chlorination system, the base metal and the
precious metal are leached together, which makes the composition of
the leaching liquid complicated and difficult to separate. H2O2 can also
be used as an oxidizer to convert Se and Te in CAS (Xu et al., 2020). In a
weak acid system, using H2O2 as oxidant can avoid the oxidation
roasting process, shorten the technological process and production
cycle, and enhance metal recovery. However, the acid leaching of Cu
often causes the loss of Ag and Te, hence, a certain amount of sodium
chloride is often added in the leaching process to precipitate Ag in the
form of silver chloride(AgCl), whereas Te in the leaching solution is
suitable for replacement with Cu powder. The recoveries of Se and Te
using this method are 99% and 98%, respectively, and the loss rate of
precious metals is less than 0.1%.
3.2. Separation of Se and Te
Selenide or telluride-containing leachate is the main raw material
for extracting Se or Te through the extraction method described in
Section 3.1. The separation of Se or Te from the solution mainly in-
cludes neutralization precipitation and reduction method, as shown in
Table 4. The composition of reducing products depends not only on the
reducing behavior of various metal ions but also on the reducing ability
of the reducing agent (Zhang et al., 2017b). The methods for separating
Se or Te from solution also include the solvent extraction
(Bandyopadhyay et al., 1996; Mandal et al., 2004), resin adsorption
6
Hydrometallurgy 197 (2020) 105460
Table 4
Electrode reactions and characterization of various reductants (25 °C).
Ion/reductant Electrode reaction Standard electrode
potential, φΘ/V
H2SeO3 H2SeO3 + 4H++4e = Se+3H2O 0.740
H3TeO3+ H3TeO3+ + 3H++4e = Te+3H2O 0.558
H4N2·H2O N2 + 2H2O + 4H++2e = 2HONH3+ −1.87
Zn Zn2++2e = Zn −0.763
Fe Fe2++2e = Fe −0.44
HONH3Cl N2 + 5H++4e = H2NNH3+ −0.23
SO2 SO42− + 4H++2e = SO2 + 2H2O 0.138
Cu Cu2++2e = Cu 0.34
(Betti et al., 1997; Rhee et al., 1999; Wang and Fthenakis, 2005), mi-
crobial (Brierley and Brierley, 1999) and liquid membrane separation
methods (Chakraborty and Datta, 1996; Hoffmann, 1989). However,
there are few separation methods that have been successfully applied
for the separation and enrichment of Se or Te in CAS.
The neutralization precipitation method mainly uses alkaline solu-
tions such as sodium hydroxide or sodium carbonate to adjust the pH of
the Cu separation solution after leaching of CAS to 3–4 so as to obtain
tellurium dioxide precipitation. The process is relatively mature in
terms of industrial application; however, a large number of sodium ions
is added in practice, and thus, the solution cannot be directly used to
produce copper sulfate products. Sulfuric acid is used as a neutralizer to
recover Te from alkaline solutions. The main reaction is as follows:
Na2TeO3 + H2 SO4 = TeO2 + Na2SO4 + H2 O (28)
An active metal or a compound with a low redox potential can be
used as a reducing agent to reduce high-valent Se, Te and other sub-
stances. This method is called the reduction method (Zhang et al.,
2017b). Commonly used reducing agents are shown in Table 4.
According to Table 4, the electrode potentials of H2SeO3 and
H3TeO3+ are 0.740 and 0.558 V, respectively. By comparing the elec-
trode potential between the reducing agent and the metal ions, it can be
found that all of the candidates in Table 4 satisfy the requirements of
the reduction reaction. Therefore, it can be concluded that Se and Te
can be recovered from the solution by using Zn, Cu, SO2, Fe, H4N2·H2O
or HONH3Cl as reducing agents (Guo et al., 2017). Table 5 shows the
main methods of extracting Se and Te from solution. (See Table 6.)
Se and Te are not only valuable scattered elements but also harmful
elements in the production of precious metals. Therefore, during the
extraction and separation of Se and Te, the separation of precious
metals should be minimized (Dong et al., 2020). Meanwhile, the in-
termediate products rich in Se and Te obtained by the extraction and
separation of CAS need to be further processed via physical and che-
mical methods to attain high-purity or ultrapure Se and Te. Therefore,
removal of Se and Te intermediate products needs to be further in-
vestigated in depth to achieve high-value utilization of CAS (Prasad
et al., 2005; Roumié et al., 2006; Sun, 2011; Zhang et al., 2014b).
4. Extraction and separation methods of Au
Au is a strategic precious metal with special properties and im-
portant applications (Dai et al., 2012).As global consumption of Au
continues, its reserves are being rapidly depleted (Palacios et al., 2019).
At present, Au as a precious metal is inherently in short supply, with the
grade of primary resources typically less that 1 g/t. Therefore, sec-
ondary sources such as CASs are valuable additional resources (Dönmez
et al., 1999). The extraction of Au from CAS has long been based on
pyro-metallurgical method, but because of its disadvantages, such as
high cost, long technological process, and serious environmental pol-
lution, it has gradually been replaced by hydrometallurgy (Li et al.,
2015b). For a long time, Au extraction from CAS was mainly based on a
cyanide leaching process, which became increasingly unpopular due to
G. Liu, et al. Hydrometallurgy 197 (2020) 105460

Table 5
Main separation methods of Se and Te.
Raw material Methods Reaction conditions Recovery References

Decopper solution Cu replacement The excess coefficient of copper powder: 2.0, 90 °C, 2 h Se ≥ 99% (Hu and Wu, 2014)
Te ≥ 75%.
Decopper solution SO2 reduction 60 °C, 2 h, the SO2 flow rate: 0.3 L/min Se ≥ 99% (Hu and Wu, 2014)
Te ≥ 83%.
Sodium sulfide leach solution Na2SO3 + Na2S excess coefficient: 1.0 Na2S, 1.75 Na2SO3, 50 °C, 30 min 95% Te (Xu et al., 2020)
Decopper solution Na2SO3 reduction 10 g/L of Na2SO3, 75 °C,2 h. Se ≥ 99% (Zheng and Chen, 2014)
Te ≥ 98%.
Degoldized solution H4N2·H2O + H+:4.305 mol/L, 85 °C, 5 h Se 97.6% (Zhang et al., 2017b)
HONH3Cl H4N2·H2O: 0.2133 mol/L, HONH3Cl: 1.5116 mol/L. Te 100%.

its toxicity and differential cost of recovery from solution (I.e. separ-
ating the Cu-Au-Pd-Ag cyanide complexes is expensive and inefficient.)
(Han et al., 2020; Senanayake, 2004). Researchers have gradually de-
veloped some non-cyanide replacement systems, including sulfuric
acid, nitric acid, hydrochloric acid, ammonia leaching, thiourea system,
thiosulfate system solvent extraction (D Nmez et al., 2001; Grosse et al.,
2003; Puvvada and Murthy, 2000) also alkaline amino acids, in parti-
cular glycine, which can dissolve Au and Ag at pH > 10 (Oraby and
Eksteen, 2015).
4.1. Extraction of Au
In recent years, aqueous chlorination has been used to recover Au
from CAS because it produces a higher dissolution rate than cyanide
leaching (Li et al., 1991). The most commonly used chlorination sys-
tems are HCI–NaCl and H2SO4–NaCl systems (Ding et al., 2017). During
the leaching process, Au in elemental form is oxidized to a soluble
chloride complex, whereas Ag is precipitated in the form of AgCl in the
leaching residue, realizing the preliminary separation of Au and Ag
(Dönmez et al., 2001). In addition, different experimental parameters in
the leaching system affect the leaching effect of Au, such as the type and
concentration of the leaching agent, solid/liquid ratio, stirring speed,
and temperature. These parameters should be co-optimized to achieve
the maximum yield of Au dissolution (Yavuz and Ziyadanoğullari,
2000).
Au leaching by chlorination from CAS is a gas–liquid–solid poly-
phase reaction (He and Xu, 2015). The solubility of non-polar chlorine
gas in a polar solution is very low, which decreases with increasing
temperature (Liddell and Adams, 2012). As a result, most of the
chlorine gas escapes from the system, causing environmental pollution
and endangering human health. NaClO3 can solve the above problems.
NaClO3 is easily soluble in water and generates ClO2 and Cl2 with
strong oxidizing and chemical activity in acidic solutions, which in-
creases the solution potential and promotes the leaching of Au.
Therefore, it is often used as an oxidant in Au leaching. In addition to
the typical oxidants of chlorine gas and NaClO3, other studies have been
carried out on the basis of an acid + oxidant system, as shown in Fig. 5
(Geoffroy and Cardarelli, 2005). Typical oxidizers are as H2O2 (Zhang
et al., 2010),. NaClO (Li et al., 2015b; Senanayake, 2004) and HNO3
(Sheng and Etsell, 2007; Wang et al., 2016).
Although these reagents can be used as oxidants to leach Au from
CAS, the process is characterized by certain disadvantages such as low
leach rate, high energy consumption, serious pollution, and poor se-
lectivity to impurity ions (Gui et al., 2016). During Au chlorination
leaching, many impurities dissolve into the solution together with Au,
making subsequent Au extraction difficult (Hasab et al., 2014; Xu et al.,
2014). Therefore, impurities such as Cu, Pb and other metals need to be
removed before leaching Au from CAS. Typically, CAS is acidified with
HCl to remove some base metal sulfides prior to Au leaching, or sodium
chloride is added to precipitate Ag during the leaching process, fol-
lowed by an oxidizer to leach Au. However, the control potential
leaching method can partly overcome this shortcoming. If the im-
purities in CAS cannot be removed before leaching Au, its leaching rate
will be low, regardless of the oxidizer added.
Thiosulfate and thiourea leaching of precious metals from raw ores
and other metallurgical intermediates are the most promising leaching
systems, mainly due to the low environmental risk, low energy con-
sumption, and good selectivity (Chauhan et al., 2018; Ding et al.,
2019a). However, these methods are rarely used for CAS (Aazami et al.,
2014; Lampinen et al., 2015; Xu et al., 2016b). Xu et al. (2016a) studied
the leaching of Au, Ag, and Pd from CAS using the thiosulfate system,
and discussed the influence of PbO impurity on the leaching effect.

Table 6
Au leaching system from CAS.
System Conditions Result (extraction yield, Reference
%)

HCl + H2O2 75 °C, 2 h; stirring speed: 200 rpm, particle size: 100 μm, Au 100% (Wei and Man, 2017)
HCl: 4 M, H2O2: 0.1 M
HCl + NaClO 90 °C, 2 h; stirring speed: 200 rpm; particle size: 100 μm Au 100% (Wei and Man, 2017)
HCl 3 M, NaClO 0.054 M
H2SO4 + NaClO3 NaClO3 3.75 g/L, NaCl 0.02 mol/L, H2SO4 0.5 mol/L, 80 °C, 3 h, L/S: 5:1 Au 98.1% (Ding et al., 2017)
HCl + HNO3 Pulp density: 10 g/L, 25 °C; stirring speed: 200 rpm; particle size: 100 μm, 2 h, aqua Au 100% (Wei and Man, 2017)
regia: 75 mL HCl + 25 mL HNO3, NaCl: 0.5-1 M
Au–NH3–S2O32−–H2O 1 × 10−4 M precious metal/0.01 M base metal elements,0.6 M S2O32−,1.0 M NH3, 25 °C Au 88.0% (Xu et al., 2016a)
and 101.3 kPa pressure
EmimHSO4 80%(v/v) [Bmim]HSO4, 75 °C, 4 h and solid/liquid ratio: 1/25 g/mL Au 89.07% (Rüşen and Topçu, 2017)
EmimHSO4 80% (v/v) [Bmim]HSO4 at 95 °C,4 h, pulp density at 40 g/L. Au 97.32% (Aydın and Mehmet Ali, 2018)
CS(NH2)2 + Fe3+. thiourea: 10 g/L, Fe3+: 5 g/L; pH: 1.0; 30 °C, 2 h Au 99.6% (Yavuz and Ziyadanoğullari,
2000)
Thiourea+H2O2 CS(NH2)2/H2O2: 2/1 g/L, pH: 1.2–1.4. Au 99.99% (Ranjbar et al., 2014)
Cl2 60 °C, 4500 s, stirring speed: 600 rpm, solid/liquid ratio: 0.1 g/mL Au 99%. (Dönmez et al., 2001)
H2SO4+ MnO2 H2SO4: 20 V%, L/S: 10:1, MnO2: 1.25 g, NaCl: 3 g, 40 °C, 40 min Au 77% (Hait et al., 2002)
Cl2 + HCl 180 min, 210 rpm,Cl2: 1.99 L/ min, L/S: 12.57 L/ kg, HCl: 2.74 mol/ L Au 93% (Saeedi et al., 2015)
HNO3 + HCl Acid/alcohol ratio: 4, extractant: 0.5 M, Aqueous/ alcohol ratio: 5, pH 10.5 Au 81%. (Dehghanpoor et al., 2016)

7
G. Liu, et al.
Fig. 5. Hydrometallurgical method for recovery of Au from CAS.
Under optimal conditions, the recovery of this precious metal reached
88.0%. However, thiosulfate solutions have poor stability and may
decompose in reaction systems (Syed, 2010). Further, high reagent
consumption makes thiosulfate systems uneconomical (Aylmore and
Muir, 2001; Xu et al., 2016a). Yavuz and Ziyadanoğullari (2000) stu-
died the recovery of Au from anode slime in thiourea system. The study
showed that the removal of Cu, Te, Se, and most Ag is a prerequisite for
efficient extraction of Au. Ranjbar et al. (2014) used a thiourea solution
to completely dissolve Au in the anode slime, but thiourea is easily to
decomposed in the presence of oxidizing metal ions such as Cu2+ and
Fe3+, resulting in high reagent consumption. Moreover, leaching is
normally carried out in the pH range of 1–2, because, although the
reagent is fairly stable thermodynamically in acid and neutral mediums,
it decomposes rapidly in alkaline solutions. The impurity concentration,
redox potential, and leaching time in the leaching system need to be
strictly restricted (Li et al., 2012).
4.2. Separation of Au
Because of the high electrode potential of Au, it is easily reduced by
a reducing agent; however, the reducing agent selected should not be
too strong, otherwise other impurities in the solution will also be
8
Hydrometallurgy 197 (2020) 105460
reduced (Behnamfard et al., 2013). In recent years, considerable re-
search has been conducted on the separation and enrichment of Au
from Au-containing leaching solutions. Oxalic acid, formaldehyde,
sulfur dioxide, sodium sulfite, boric acid, and active metals are com-
monly used as reducing agents of precious metals (Fleming, 1992;
Karavasteva, 2010; Li, 2000; Wang et al., 2007).
The reducing electrode potential of H2PtCl6 and H2PtCl4 is much
smaller than that of HAuCl4, whereas the reducing electrode potential
of SO2 is between that of Au, Pt, and Pd. Therefore, using SO2 as a
reducing agent can selectively reduce Au, whereas Pt, Pd, and other
impurities remain in solution. Oxalic acid has the characteristics of
rapid reduction and good selectivity, and it can obtain Au powder with
a purity of more than 99.99%, which is higher than that obtained by
SO2 reduction.
Cu and Zn, which are more active than Au, are often used to replace
Au in chlorinated leaching solutions. Dönmez et al. (2001) used a ro-
tating copper disc to replace Au in a chlorinated solution. The effects of
temperature and rotation rate on the replacement effect were mainly
investigated, and kinetic analysis of the replacement process was also
carried out. The results showed that the pH of the Au-containing
chlorinated solution of 1.5 was favorable for the Au replacement re-
action and that the replacement process was controlled by diffusion.
G. Liu, et al.
At present, sodium sulfite as a reducing agent is mainly used for
industrial reduction of Au, but the process requires temperatures of
approximately 75 °C; this causes the consumption of high amounts of
energy (Yu et al., 2014). Additionally, a large amount of SO2 is also
produced during the reduction process which pollutes the environment.
When sodium sulfite is used as the reducing agent, a small amount of
impurities such as sodium ions are introduced in the reaction process to
generate corresponding salts such as Na2SO4 and NaCl, which affect the
quality of the Au powder (Nie et al., 2015).
Hydrazine hydrate is a highly reductive liquid reducing agent that
can reduce many metal salts to metal elements under different acidity
conditions and is commonly used to reduce precious metals (Hao et al.,
2018). Under acidic conditions (pH = 1.5), hydrazine hydrate easily
reduces Au. During the reduction process, hydrazine hydrate is oxidized
into nitrogen and water, releasing hydrogen ions.
In addition to the reduction methods mentioned above, extraction
and ion adsorption methods are also commonly used to extract Au from
solution (Xing et al., 2018). Dibutyl carbinol (DBC) and Tri-butyl sulfate
(TBP) can extract Au from chlorination systems, and nanoparticles (NP)
can extract Au from thiourea leaching systems (Bae et al., 2020;
Ranjbar et al., 2014; Sadeghi and Alamdari, 2016). However, these
methods are currently in the research stage, and large-scale industrial
production has not been reported to date.
5. Extraction and separation methods of Ag
Pyrometallurgy is the traditional method of recovering Ag from CAS
and other secondary resources (Cui and Zhang, 2008). First, the pre-
cious metal–lead alloy is produced by high-temperature reduction
smelting. Then, the obtained alloy is oxidized and smelted to remove Pb
and produce Au–Ag–Pt alloy. Finally, Ag and Au are obtained by
electrolysis (Li et al., 2019). However, this method is usually char-
acterized by high energy consumption, poor quality of recovered Ag,
and serious air pollution during the recycling process (such as the
presence of SO2, Pb, As, and Sb in the soot). To address these short-
comings, some hydrometallurgical processes have been developed
(Khaleghi et al., 2014; Ludvigsson and Larsson, 2003; Schulze, 1984; Xu
et al., 2016a) as shown in Fig. 6.
5.1. Extraction of Ag
In the process of recovering Ag from the hydrometallurgy of CAS,
Ag is converted to AgCl; otherwise, the Ag needs to be oxidized and
transformed (Xiao et al., 2018). Therefore, in theory, any reagent that
dissolves AgCl can be used as the leaching agent for Ag. In current in-
dustrial production, the hydrometallurgy for recovering Ag from CAS
mainly includes ammonia leaching, sodium sulfite, thiosulfate, and
nitric acid leaching methods, as shown in Table 7.
Ag in CAS was extracted by nitric acid leaching, which was first
applied by the Taiwan Institute of Nuclear Energy Research (INER),
with a recovery rate of 99% (Chen et al., 2015). The leaching process
produces Ag containing a nitric acid solution with a high impurity ion
content, resulting in Ag dispersion and longer process flow. Ammonia
leaching can solve this problem well. At room temperature, AgCl is
easily dissolved in ammonia water to form silver–ammonia complex
ions ([Ag(NH3)x]+(x = 2, 3, 4), where the value of x is determined by
the concentration of ammonia in the leaching system (Blauth et al.,
2010; Eksteen and Oraby, 2015). Leaching of Ag is often accompanied
by Pb removal. Usually, ammonium carbonate or alkali powder is
added to convert the lead in the material into lead carbonate, and
which enters the leaching residue (Fox et al., 2002). This method is a
convenient operation with a high leaching rate, and is widely used in
industry (Sansotta and Zahn, 2017). However, ammonia volatilization
results in a poor operating environment, and ammonia cannot be re-
cycled.
To solve the shortcomings of the ammonia leaching system, a
9
Hydrometallurgy 197 (2020) 105460
sodium sulfite leaching system is used for leaching Ag from CAS. The
leaching of Ag in the sodium sulfite system is greatly affected by pH
(Syed, 2016). In a solution with a pH value of 5.5–6-5, sodium sulfite
reacts with AgCl quickly to form silver sulfite, whereas complex ions
containing Ag are generated when the pH is 7–8. When the pH is
greater than 9, the sulfite is relatively stable, which has little impact on
the leaching effect of silver. Therefore, the pH of the reaction system
should be strictly controlled for leaching Ag from CAS using sodium
sulfite.
In addition to AgCl, Ag usually exists in the form of Ag2S and Ag2O,
which can be dissolved by thiosulfate. Copper ions are usually added as
catalysts in thiosulfate systems, but sulfuric acid and sodium sulfate are
often produced, consuming large amounts of sodium thiosulfate.
Adding sodium sulfite in the system can reduce the amount of sodium
thiosulfate, and thereby reduce the generation of sulfuric acid and so-
dium sulfate. The reactions are as follows:
3
2CuSO4 + 2Na2S2 O3 + 3H2 O + = Cu2 S + 3H2 SO4 + 2Na2SO4
2O2
(66)
2CuSO4 + 4Na2S2 O3 + Na2SO3 + H2 O
= 2Na3 [Cu(S2 O3 )2] + H2 SO4 + 2Na2SO4 (67)
Na2SO3 + S = Na2S2 O3 (68)
When choosing the Ag leaching method, the occurrence state and
content of Ag in CAS should be considered. For CAS with complex
morphology and a high Ag content, the nitric acid leaching method can
be used to improve the leaching effect of silver, whereas for CAS with
AgCl as the main form, sodium sulfite or ammonia leaching method
should be selected (Amer, 2003; Chen et al., 2015). In addition, the
combined order of the extraction and separation of Au and Ag is de-
termined by the morphology of Ag. If Ag is not sufficiently chlorinated,
the recovery of Au should be prioritized over that of Ag.
5.2. Separation of Ag
The reducing agents of silver chloride include hydrazine hydrate,
formaldehyde, and active metals, among others. Formaldehyde is a
toxic substance that causes environmental pollution problems and im-
purities are easily introduced with active metal replacement (Liang,
2012). Hydrazine hydrate, however, has the advantages of high re-
duction efficiency, short reaction time, and clean environmental pro-
tection, and it does not introduce other impurities.
Under the condition of 7.7 < pH < 13.5, ammonia and silver ions
form stable Ag[NH3]2+ complex ions in the solution (Ni et al., 2014).
However, when the solution pH is greater than 13.5, the complex is
precipitated as Ag2O. Therefore, the pH of the Ag component should be
controlled below 13.5, and the main reaction formula is as shown in
Fig. 6.
The reduction capacity of formaldehyde in sodium sulfite solution is
related to the pH of the solution, which can be clearly seen from the
following reactions (Li, 2001):
In an acidic solution:
H2 CO3 + 4H+ + 4e = HCOH + 2H2 O = 0.05V (69)
HCO3 + 5H+ + 4e = HCOH + 2H2 O = 0.044V (70)
CO32 + 6H+ + 4e = HCOH + 2H2 O = 0.197V (71)
In an alkaline solution:
HCO3 + 3H2 O + 4e = HCOH + 5OH = 0.989V (72)
CO32 + 4H2 O + 4e = HCOH + 6OH = 1.043V (73)
The greater the pH of the solution, the stronger the reduction ability
of formaldehyde; hence, the reduction of silver with formaldehyde must
G. Liu, et al. Hydrometallurgy 197 (2020) 105460

Fig. 6. Hydrometallurgical method for recovery of Ag from CAS.

be carried out at a high pH.
Hubin (Hubin et al., 2007) studied the electrodeposition of silver
complexes from thiosulfate solutions, which was unaffected by acidity
compared to other methods (Freitas et al., 2017; Staroń et al., 2017).
Active metals are often used to extract Ag from solutions (Kuntyi
et al., 2013). However, the main disadvantages of this method are the
low current efficiency caused by the low concentration of precious
metals and the high concentration of Cu used as an oxidant in thio-
sulfate leaching systems (Alonso et al., 2008).
Through a literature review, we found that these methods have not
been applied to recovering Ag from CAS on a large scale. A possible
reason is that the leaching process of CAS is complicated because one
needs to consider the interference of various impurities and the stability
of the system. Therefore, it is necessary to consider the presence of Ag
in CAS and the stability of the leaching system in order to develop
various methods for recovering Ag from CAS(Lu et al., 2020).
6. Extraction and enrichment of Pt and Pd
Because of the high content of PGMs in secondary resources such as
spent catalysts and CAS, they have become the main source of PGMs
(Saguru et al., 2018). Recovery PGMs from spent catalysts has been
widely investigateds (Ding et al., 2019b; Firmansyah et al., 2019; Zhang
et al., 2019a). Unlike spent catalysts, the recovery of PGM from CAS is
usually done after the separation of the base metals Cu, Pb and Zn, and
the precious metals Au and Ag.

Table 7
Ag leaching system from CAS.
System Conditions Results Reference

Thiosulfate 0.025/0.035/0.050 M thiosulfate, 3 min 94%–96% Ag (Xiao et al., 2018)

H2SO4 roasted + H2O 247 °C, L / S 1.95 96.48% (Khanlarian et al., 2019)
Ammonia 2.94 M ammonia,300 min 89% Ag (Fox et al., 2002; Sansotta and Zahn,
2017)
NH3 + S2O32− + H2O 0.6 M S2O32−,1.0 M NH3, 25 °C and 101.3 KPa pressure. 93.4% Ag (Xu et al., 2016a)
S2O32− + H2O + Microwave ammonium thiosulfate 0.4 M, 313 K, solid/liquid ratio 1/10, 90 min, and stirring 88.76% Ag (Tokkan et al., 2013)
speed 500 rpm.
HNO3 60–90 °C，180 min, HNO3 1-4 M 96% Ag (Khaleghi et al., 2014)
(Thiourea+Fe3+ thiourea 10 g/l, 5.0 g/L ferric ion 60 °C, 30 min 92.2% Ag (Amer, 2003)

10
G. Liu, et al.
Fig. 7. Hydrometallurgical method for recovery of Pt and Pd from CAS.
In general, during the hydrometallurgical treatment of CAS, espe-
cially the chlorination of Au, Pt and Pd almost all enter into the
chlorination liquid with Au, forming chloroplatinic acid and chlor-
opalladium acid, respectively, and only a small amount of Pt and Pd
remains in the chlorination leaching residue (Mpinga et al., 2015). In
platinum–palladium chloride solutions, Pt and Pd concentrates are
obtained via xanthate precipitation, activated carbon adsorption, am-
monium chloroplatinate and dichlorodioxide–palladium precipitation,
ammonium chloride precipitation in a platinum–ammonia solution,
palladium, copper powder or zinc powder replacement, ion exchange,
extraction, and other methods (Jha et al., 2013; Nowottny et al., 1997),
as shown in Fig. 7.
The traditional method of separating palladium from the chlorina-
tion leaching solution of CAS is ammonium chloride precipitation
(Wang et al., 2012). By adding ammonium chloride into the chlorina-
tion solution (after Au reduction) as an oxidant, Pt2+ can be selectively
oxidized to Pt4+ to form slightly soluble (NH4)2PtCl6, whereas most
Pd2+ and other impurities remain in the solution without reacting with
ammonium chloride. The (NH4)2PtCl6 is calcined at a high temperature
to obtain sponge Pt having a purity of more than 99.95%. After Pt se-
paration, the base metal can be removed and Pd(NH3)2Cl2 can be ob-
tained by controlling the addition of ammonia. Pd sponge products with
purity of 99.95% or more can be obtained by the reduction of Pd
(NH3)2Cl2 with hydrazine hydrate. This method can be used to obtain
relatively pure Pd, which is generally used in chlorinated liquids with
high Pd content or in the purification of crude Pd.
The chlorinated liquid containing Pt and Pd with high chlorine
content has a large number of impurity elements such as Cu, Fe, Zn and
some soluble SPMs (Damien et al., 2020). The impurity elements can be
hydrolyzed and precipitated by adjusting PH, and then the Pt and Pd
can be precipitated by sulfur dioxide.
The xanthate precipitation method selectively precipitates Pt/Pd
from the leachate with butyl xanthate (Pan et al., 2018). In the hy-
drochloric acid/nitric acid system, Pt/Pd can form the corresponding
xanthate precipitate with xanthate.
The xanthate solution is stable in the pH range of 6.5–7.5, but it
partially decomposes into carbon disulfide and alcohol in acidic
11
Hydrometallurgy 197 (2020) 105460
solutions (Cheng and Luo, 2016). The reaction equation is as follows:
ROCSS + H+ = CS2 + ROH (88)
Therefore, xanthate is not suitable for use in strongly acidic media,
but the reaction rate of xanthate with Pt/Pd plasma is much faster than
the decomposition rate in acidic solution. Therefore, Pt, Pd, and other
precious metals can be precipitated using strong and weak acidic so-
lutions (Cheng and Luo, 2016). Xanthate precipitation is characterized
by good selectivity, simple operation, and low cost. Therefore, it is the
most suitable method for enriching Pt/Pd.
The main chemical properties of PGMs are their chemical stability
and the variety of their complexes (Harjanto et al., 2006; Mahmoud,
2003). The redox potential of PGMs is behind that of hydrogen. They
are chemically inert metals, that is, they can hardly lose electrons to be
oxidized into cations, so they have very superior electrochemical sta-
bility. However, once PGMs are converted into cations, they have a very
high oxidation potential and become very strong oxidizers. It is easy to
replace them from the solution with common electronegative metals
such as Cu, Zn, Pb and other reducing agents, which has become an
important method to recover them from the solution (Guo et al., 2010).
The traditional precipitation method can only achieve high recovery
rates when the concentration of noble metals in solution is high or the
content of impurity elements is low, and so they are mainly used for the
enrichment of crude Pt and Pd. Solvent extraction, activated carbon
adsorption, and ion exchange methods, as new methods for the ex-
traction of PGMs, have successfully made up for this shortcoming
(Zhang and Zhang, 2014). They can extract Pt and Pd from solutions
with low concentrations of precious metals. The specific process de-
pends on the content of Pt and Pd in the precious liquid and the type
and content of base metal impurities, as well as the extraction agent
used. At present, the recovery rate of Pt and Pd from platinum and
palladium concentrate is not high, and there are some shortcomings,
such as high content of Pt and Pd in the tailings and the high content of
impurities in the finished products (Mpinga et al., 2015). These pro-
blems are worthy of further study.
G. Liu, et al. Hydrometallurgy 197 (2020) 105460

7. Recovery potential and economic evaluation of copper anode Table 8

slime Market prices of SPMs (available at https://www.lme.com/en-GB/CN/The-
metals).
With the rapid development of the electrical revolution and the Elements(i) Bi(g/t) Purity Pi(RMB/g)
information revolution, Cu plays a more important role in the new
development period because of its high thermal and electrical con- Au 2100 99.99% 279.04
Ag 104,500 99.99% 3.31
ductivity, strong chemical stability and corrosion resistance, and
Pt 300 99.99% 175.07
greater plasticity and ductility (Sverdrup et al., 2014a; Sverdrup et al., Pd 95.3 99.99% 276.35
2014b; Zhang et al., 2019b). According to statistics, more than 90% of Se 52,200 99.99% 0.21
industries need Cu products, including important basic supporting in- Te 5800 99.99% 0.485
dustries in the development of the national economy such as electric
power (Moreno-Leiva et al., 2020), electronic appliances (Schipper
et al., 2018), transportation (Li et al., 2017c) and construction (Wang of CAS, Bi: content of each element in CAS, Pi: price of each element, Qi:
et al., 2018). Copper resources have also become an important strategic annual value of each element in CAS, i: Au, Ag, Pt, Pd, Se and Te, j:
resource related to national economic and social security (Wang et al., year.
2013). At present, more than 80% of the world's Cu is obtained by As can be seen from Fig. 9, the CAS produced annually contains
electrolytic refining, which inevitably produces a large amount of CAS. more than 136 t of Au, 20 t of Pt, 6 t of Pd, 370 t of Te, 33.9 million tons
At present, China's refined Cu production and Cu resource consumption of Se, and 67.8 million tons of Ag. If all these SPMs could be extracted,
rank first in the world, occupying a pivotal position in the global Cu it would greatly reduce the mining of raw ore, and greatly save re-
industry (Li et al., 2017c).This paper takes the annual output of refined sources and energy.
Cu (available at http://www.stats.gov.cn) in China as an example to Through calculation and analysis, we found that the elements with
analyze the recovery potential and economic value of CAS. the highest economic value in CAS are Au, Ag, Pt, Pd, Se, and Te in
According to statistics, in the past six years, as shown in Fig. 8, order, as shown in Fig. 10. Although CAS contains less Au, Pt, and Pd,
China's refined Cu production has rapidly grown from 6.49 million tons these elements have the most economic value, especially Au, which
in 2013 to 9.03 million tons in 2018 (available at http://www.stats. accounts for almost half of the recovery value of CAS. Therefore, the
gov.cn). The output of recycled Cu in China has remained at around 3.0 ultimate goal of CAS recovery method is to recover the precious metals.
million tons, accounting for 35% of refined Cu production (Shuva et al., If the CAS produced each year had been recovered, the economic value
2016). It can be seen that Cu-containing waste has become an im- from it would have been close to ¥66.5 billion in 2013 alone and close
portant source of Cu resources in China (Chen et al., 2019). to ¥93 billion in 2018.
According to China's annual production of refined Cu published by The content of SPMs in CAS is much richer than that of natural ores.
the National Bureau of Statistics, the annual output of CAS in the last six There is an urgent need to recover precious metals from CAS in terms of
years was estimated. One percent (1%) of anode slime is produced for profit prospects by environmentally friendly and economic recovery
each ton of refined Cu produced. For convenience of comparison and methods. At the same time, efficient recycling of CAS can reduce our
calculation, we selected a representative CAS with a moderate noble exploitation of natural resources, avoid water and air pollution, and
metal content as a reference: Au 0.21%, Ag 10.45%, Pt 300 g/t, Pd reduce greenhouse gas emissions, in addition to providing economic
95.3 g/t, Se 5.22%, and Te 0.585%. Although CAS contains large benefits. Furthermore, the recycling of these materials would also re-
amounts of Cu, Pb, Zn, etc., they are conventional metals, and so their duce the volume of the solid waste generated. Comprehensive analysis
economic value is not evaluated in this paper. The market price of shows that the recovery of SPMs from CAS has great recovery potential
precious metals is derived from London Metal Exchange (available at and considerable economic value.
https://www.lme.com/en-GB/CN/The-metals) and is shown in Table 8.
The content of each SPM and its economic value in CAS were calculated 8. Future recycling strategy and perspectives for copper anode
respectively using Eqs. (89) and (90) and the results are shown in Fig. 9. slime
Cij = Yi Bi (89)
At present, pyrometallurgical or hydrometallurgical pretreatment
for recovering Cu, Zn, Ni, Pb and other base metals in CAS is relatively
Q ij = Cij Pi (90)
mature and has been applied in various Cu smelters. Regarding the
Ci: annual production of each element in CAS, Yi: annual production recovery of SPMs, although the recycling system is rich, its industrial

Fig. 8. Production of primary and recycled refined copper in China.

12
G. Liu, et al.
Fig. 9. Annual production of SPMs in CAS.
application presents challenges. As described in Sections 3–6, hydro-
metallurgical recovery methods of SPMs in CAS have been improved
and upgraded based on traditional methods. In the future, the devel-
opment and application of CAS will focus on the following aspects:
Process optimization control: Affected by the characteristics of
raw materials, CAS has an uncertain composition and diverse pro-
duction processes. It is necessary to establish a multi-objective,
multi-parameter, and elastic closed-loop cooperative control system
based on the existing technology. For example, the simulation of
optimal control technology could be introduced into the hydro-
metallurgical process. Through the optimization and control of the
entire process, such as leaching, separation, and displacement/ex-
traction of SPMs, the process can be streamlined, recovery rate
improved, and waste generation reduced.
Technology development and collaborative disposal: Based on
the existing problems of CAS recovery technology, such as low
precious metal recovery rate, high consumption of chemical agents,
large amount of waste water and residues, new metallurgical
methods such as metal–organic frameworks (MOFs), supercritical
technology, vacuum metallurgy technology, biological metallurgy,
ion exchange technology, and electrochemical technology should be
developed. Moreover, in the process of treating CAS, the colla-
borative disposal of metallurgical wastes containing low-grade
precious metals should be given more attention. It is necessary to
gradually introduce non-ferrous metal smelting intermediate pro-
ducts with large output, such as copper smelting ash, copper sludge,
Fig. 10. Value of SPMs in CAS.
13
Hydrometallurgy 197 (2020) 105460
and thermal cracking slag, so as to realize the application and ex-
pansion of the process technology and the collaborative disposal of
raw materials.
Environmental and policy assessment: As the pattern of the
copper smelting industry has changed, raw materials have gradually
introduced secondary resources such as recycled copper, resulting in
the complex composition of CAS and increase of environmental
risks. Supply risk and environmental risk analysis can be carried out
for specific processes and SPMs. Common analysis methods include
the Herfindahl–Hirschman Index (HHI), Environmental
Performance Indexes (EPI), Life Cycle Assessment (LCA), etc. While
ensuring high-efficiency recovery and complete separation of SPMs,
the recycling process is environmentally friendly and sustainable. In
view of the current extensive treatment mode of CAS, industry
standards should be strengthened and the disposal of CAS should be
standardized to reduce policy risks. Meanwhile, the government
should strengthen the supervision of CAS recycling enterprises and
implement a loose tax policy to facilitate the sustainable develop-
ment of a CAS processing industry.
In short, CAS has rich metal resources and great economic value. A
high recovery efficiency, a harmless disposal process, a circular
economy, and sustainability are the mainstream trends of recovering
SPMs from CAS in the future.
G. Liu, et al.
9. Conclusion
In recent years, CAS has been widely studied because it is rich in a
large number of SPMs. Scholars in various countries have successively
developed various extraction and separation methods of scattered me-
tals, such as traditional pyrometallurgy, gradually improved semi-hy-
drometallurgy, and novel hydrometallurgical processes such making
use of benign (edible) organic acids, and reducing agents and com-
plexing agents, which have been gradually put into practical applica-
tion. Although there are many methods, it is still not enough to sys-
tematically classify and summarize the extraction and separation
methods of SPM in CAS. Therefore, based on the investigation of a large
number of studies and study of the mineral composition of CAS, this
paper offers a detailed analysis and summary of the recovery principle
and methods of typical SPMs from CAS. Various process conditions
were also analyzed in order to make better use of resources.
In the long run, the novel hydrometallurgical process will still co-
exist with the traditional recycling process of SPMs in CAS. In parti-
cular, the combination of hydrometallurgy and pyrometallurgy can
achieve high recovery of SPMs. The new method of hydrometallurgy for
treating CAS is the development direction of small- and medium-sized
enterprises. However, some problems were gradually revealed by these
methods, such as relatively poor adaptability to raw materials and the
small scale of treatment, leading to the difficulty of large-scale appli-
cation of hydrometallurgy. Moreover, there is no solvent that can leach
all the elements in the CAS, resulting in a long process and a large
amount of wastewater treatment. One of the key chemical options is
using a combination of thermal processing followed by hydro-
metallurgical options, which will be the future improvement direction
of hydrometallurgy.
The ultimate goal of CAS recovery method is to recover the precious
metals. The CAS produced annually contains more than 136 t of Au,
20 t of Pt, 6 t of Pd, 370 t of Te, 33.9 million tons of Se, and 67.8 million
tons of Ag. If the CAS produced each year could have been recovered,
the economic value from it would have been close to ¥66.5 billion in
2013 alone and close to ¥93 billion in 2018. CAS recovery will greatly
reduce the mining of raw ore and greatly save resources and energy.
Therefore, CAS has great recovery potential and considerable economic
value.
However, as the pattern of the copper smelting industry changes,
some problems are gradually exposed in the recovery of SPMs from
CAS. Therefore, we propose to optimize the comprehensive disposal of
CAS in terms of optimal control of the recovery process, the introduc-
tion of new methods and the coordinated disposal of raw materials, and
environmental and policy reform. Through the literature review, it was
found that there are few studies on the kinetics and thermodynamics of
SPM leaching in CAS. At the same time, studies on the interference
mechanism of impurity ions on SPMs are rarely reported. Therefore,
further study on the separation and purification of SPMs in CAS is also a
research direction in the future.
In this paper, the recovery process of SPMs in CAS was compre-
hensively analyzed and summarized. However, there is no analysis on
the distribution behavior of SPMs in each process, nor is there any
comparative analysis on the economic adaptability and energy con-
sumption of each recovery process. Therefore, these will be the direc-
tion of our future research and improvement.
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.
14
Hydrometallurgy 197 (2020) 105460
Acknowledgment
This work was supported by the National Key Research and
Development Program of China (No. 2018YFC1903104,
2018YFC1903603).
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