Resources, Conservation & Recycling 168 (2021) 105366

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Resources, Conservation & Recycling

journal homepage: www.elsevier.com/locate/resconrec

Review

Comprehensive review on metallurgical recycling and cleaning of

copper slag
Hongyu Tian, Zhengqi Guo *, Jian Pan, Deqing Zhu, Congcong Yang, Yuxiao Xue, Siwei Li,
Dingzheng Wang
School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, PRC

A R T I C L E I N F O A B S T R A C T

Keywords: Copper slag, generated mainly during copper smelting, and classified as a potentially harmful waste, is an
Copper slag important secondary resource containing not only valuable metals, such as Cu, Fe, Zn, Co and Ni, in abundant
Hazardous waste quantities, but also hazardous elements, such as Pb and As. Hence, in response of its potential economic per­
Recycling
formances and environmental benefits, copper slag needs to be subjected to further metallurgical recycling and
Cleaning
Hydrometallurgical process
cleaning instead of being dumped or abandoned without treatment. Here, a critical review of the generation
Pyrometallurgical process mechanism, and chemical and physical characteristics of copper slag is provided. Details of the mainstream and
recently developed routes for metallurgical recycling and further cleaning of copper slag are also summarised,
such as flotation, leaching, and reduction roasting followed by magnetic separation, smelting reduction, and
molten modification followed by physical separation. The technical challenges and developmental bottlenecks of
the metallurgical processes are pointed out, which indicate that the improved processes characterised by high
recycling efficiency, low energy consumption, and low secondary environmental pollution continue to be the
focus of research and development in sustainable waste utilization of copper slag.

1. Introduction
Presently, copper is commonly a required metal for daily life of
humans and simultaneously indispensable for the worldwide markets. It
is generally used for multifarious applications, such as construction,
electric power, transportation, and correlated fields (Fan et al., 2014).
This resulted in the current growth trend of the demand for copper in the
last few decades (Ettler et al., 2003). The production efficiency of cop­
per, worldwide, has increased rapidly, amounting to 28.50 million tons
in 2019. At present, over 80% of global copper products is obtained via
beneficiation from copper sulphide concentrates followed by the pyro­
metallurgical process, which is characterised by high raw material
adaptability, low energy cost, and high production efficiency (Gbor
et al., 2000; Harish et al., 2011; Potysz et al., 2015). However, an un­
desirable and unavoidable slag phase will be left behind following the
recovery of metallic copper during the pyrometallurgical treatment of
copper ore concentrates (Gorai et al., 2003; Sarfo et al., 2017a; Mur­
avyov et al., 2012). Almost 2–3 t of copper slag is generated as residual
product per ton of copper product, according to the performance of the
copper concentrates and the operational condition during the pyro­
metallurgical process. The yield of slag reaches nearly 70 million tons
each year worldwide (Radetzki, 2009; Shi et al., 2008). A large pro­
portion of the copper slags are commonly throwed at the slag disposal
pit, which means that a huge space is required for dumping or disposing
such large amounts of slag ( Chen et al., 2012). In addition, the
non-protected slags will easily cause an environmental risk because they
contain increased concentrations of hazardous elements, such as Pb and
As, which may be released during the biogeochemical weathering and
physical erosion (Lottermoser, 2002; Kierczak et al., 2013; Vítková
et al., 2010). Therefore, external factors may accelerate the mobilisation
of harmful elements and their further move to soils and surface waters
(Alpa et al., 2008; Saffarzadeh et al.). Furthermore, this contamination
by hazardous elements can be harmful to various existing species. These
hazardous substances are not only poisonous and nondegradable, but
they also continually accumulate in the organisms, resulting in health
concerns and even serious diseases (Ettler et al., 2003; Gee et al., 1997).
In a nutshell, with the available spaces for dumping the copper slag
decreasing and the environmental constraints becoming more and more

* Corresponding author.
E-mail addresses: hytian@csu.edu.cn (H. Tian), guozqcsu@csu.edu.cn (Z. Guo), pjcsu@csu.edu.cn (J. Pan), dqzhu@csu.edu.cn (D. Zhu), smartyoung@csu.edu.cn
(C. Yang), yxxue@csu.edu.cn (Y. Xue), swli@csu.edu.cn (S. Li), wangdingzheng@csu.edu.cn (D. Wang).

https://doi.org/10.1016/j.resconrec.2020.105366
Received 28 September 2020; Received in revised form 9 November 2020; Accepted 19 December 2020
Available online 28 January 2021
0921-3449/© 2020 Elsevier B.V. All rights reserved.
H. Tian et al.
rigorous, the copper smelting industry is exposed to the enormous
challenge of dealing with the residual slag (Xue et al., 2009). Depending
on the current principles of waste management, disposal via abandon­
ment of copper slags is considered the least favourable selection (Ettler
and Johan, 2014; Piatak et al., 2004).
In consideration of the potential economic performances and envi­
ronmental impact of discarded copper slag, recent research has focussed
on its sustainable utilisation through reuse, rather than disposal (Manz
and Castro, 1997; Piatak and Seal, 2010;). Alternative treatments for
copper slag have been the object of multiple studies, aimed at the pos­
sibility of its application (i) as an additive to produce value-added
products in civil fields or (ii) as raw a material to recycle valuable ele­
ments through metallurgical processes (Ettler et al., 2009; Sobanska
et al., 2000). With respect to the former, in spite of its hazardous
properties, the all-round performances of copper slag, such as abrasion
resistance, good peaceability, and high stability, have been widely used
in sand-blasting, abrasive tools, cements, pavements, asphalt concrete,
tiles, abrasive materials, glass ceramics, and roofing granules (Najimi
et al., 2011; Shi et al., 2008). These applications constitute a good
method to the current situation of limited available disposal areas. The
application of copper slag as an additive for civil materials warrants an
in-depth examination, especially considering its behaviour in the target
materials, and environmental impact (Shi and Qian, 2000; Yang et al.,
2013). Thus, its utilisation may be feasible if a prior research of the
material can confirm its stability in a particular situation and prove its
relative inertness along with the immobilisation of heavy metals by the
formation of a synthetic storage material (Alp et al., 2008; Tyszka et al.,
2014). In this case, the use of copper slag as an additive would be
justifiable from a perspective of environmental protection (Gorai et al.,
2003). However, the utilization of copper slag to the production of the
aforementioned products effects the recovery of secondary resources, as
one or more valuable elements, such as Cu, Fe, Zn, Pb, Co, and Ni, are
commonly present in the slag (Ettler and Johan, 2014; Kaksonen et al.,
2011). In principle, copper slag contains Fe and Cu in the range of
30–45% and 0.5–1.2%, respectively, whose grades are higher than those
of the industrial iron (>27%) and copper (>0.4%) ores (Gorai et al.,
2003). However, the utilisation ratio of Cu from copper smelting slag is
below 12 wt.%, while that of Fe is below 1 wt.% (Cao et al., 2012;
Moura et al., 2007). In recent decades, the depletion of high-grade Fe
and Cu ores, as well as the growing demand for their resources, have
caught more attention being paid to the development of profitable
methods for Fe and Cu recovery from copper slag (Shen and Forssberg,
2003). In addition, some of the improved methods can simultaneously
recover Zn, Pb, Ni, and Co if they exist in the slag. The suggested
methods for metallurgical recycling from the slag mainly include pyro­
metallurgical processes (e.g. reduction roasting followed by magnetic
separation, smelting reduction, and molten oxidation), hydrometallur­
gical processes (e.g. chemical leaching and bioleaching), and benefici­
ation processes (e.g. flotation and magnetic separation) (Vestola et al.,
2010; Rüşen et al., 2012; Deng and Ling, 2007; Zhao et al., 2014).
Furthermore, the secondary waste obtained after metallurgical recycling
processes is not only be lower in volume, depending on the recycling of
valuable elements from the slag matrix (especially that of Fe, which has
a concentration of nearly 40 mass%), but it can also be effectively
cleaned further by the removal of heavy metals and harmful elements
(Saffarzadeh et al., 2009). The cleaned secondary waste can also be
applied as an additive in civil engineering projects, simultaneously
realising the conversion from slag dumps of potentially hazardous
wastes to innocuous materials (Shi et al., 2008; Banda et al., 2002).
Currently, metallurgical recycling and further cleaning of copper
slag is still not widely established, in spite of the progress in the man­
agement of copper slags in the past several decades. The primary pur­
pose of the paper is to provide a critical review on the metallurgical
processes available for recycling and further cleaning of copper slag. In
this review, the generation mechanism, and chemical/physical charac­
teristics of copper slag are introduced, and then the primary and lately
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Resources, Conservation & Recycling 168 (2021) 105366
developed processes for their metallurgical recycling and further
cleaning are also comprehensively reviewed. Finally, the technical
challenges and development bottlenecks of the metallurgical processes
for copper slag are summarized and corresponding prospective coun­
termeasures are elaborated, in order to provide a useful and significant
guidance for sustainable recycling of the copper slag.
2. Generation and cleaning of copper slag
Copper pyrometallurgy, which is the primary method for the pro­
duction of copper can be classified into different types, such as con­
ventional copper smelting process (e.g. blast furnace smelting,
reverberatory furnace smelting, and electric-furnace smelting), and
modern copper smelting processes (e.g. flash smelting and bath smelt­
ing) (Erust et al., 2013; Mihailova and Mehandjiev, 2010). In general, a
typical copper pyrometallurgical process includes several stages, namely
pretreatment, smelting, converting, and fire/electrorefining as illus­
trated in Fig. 1. In a continuous process, fine particles of copper ore
concentrates, usually pretreated in dry or granulated form, along with
SiO2 flux and O2 (or air) are fed into a heated smelting furnace at
1200–1300 ◦ C. Here, the sulphide reacts rapidly with oxygen, thereby
converting sulphur into SO2 gas, and then producing molten matte and
slag (Starodub et al. 2016; Kierczak et al., 2013). The high-grade matte
is further oxidised in a converter and generate blister copper and an
oxide slag. The blister copper is then transferred into a refining furnace
and generate anode copper and refining slag. The converter and refining
slags containing high content of copper are again processed in the
smelting furnace. As a result, smelting slag is produced as the main
source of copper slag in the complete copper pyrometallurgical process,
and is the cause for the loss of the primary copper (Muravyov et al.,
2012; Karwowska et al., 2015).
The smelting process can be divided into three stages, namely
decomposition of high-valence sulphide, oxidation of sulphide, and
matte smelting and slagging reaction (Fig. 1). The efficiency of matte
smelting and matte-slag separation, as well as the extent of copper losses
to slag are mainly affected by the oxidation/reduction potential, matte
grade, smelting temperature, slag composition, and slag properties
(Deng and Ling, 2007; Najimi et al., 2011). For example, silica as the
main slagging constituent is beneficial for matte-slag separation,
whereas a large amount of silica leads to an increased viscosity of slag,
with the existence of magnetite. The elevated viscosity of slag commonly
results in a mass of copper losses because of the low sedimentation rate
of copper components. Copper is also lost to slag as sulphide, in the
absence of an oxidising atmosphere present; or as oxide or silicate in an
oxidising atmosphere. Copper loss in slag commonly ranges from 0.7 to
2.3 wt.% in the industrial stage of copper matte smelting, which is a
serious problem encountered in modern and conventional copper
smelting processes. To decrease the copper loss, a cleaning furnace (e.g.
electric slag-cleaning furnace, rotary slag-cleaning furnace) is applied
after the pyrometallurgical process, followed by a drain slag smelting
furnace to clean the copper slag (Shiet al., 2008; Kierczak et al., 2013).
Based on the study, copper in the form of Cu2S, Cu2O, or Cu is commonly
lost to smelting slag via physicochemical and mechanical losses. The
former occurs for dissolved copper species, such as oxide and sulphide
forms, and the latter originates from the mechanical entrainment of
metallic copper and/or matte (Liu et al., 2009; Vestola et al., 2010).
Statistically, a majority of copper losses are caused by mechanically
entrained metallic copper and matte at lower matte grades. In the case of
a higher matte grade (> 70 wt.% Cu), most copper losses arise from
physicochemical losses (Rüsen et al., 2016; Jalkanen et al., 2003;
Yazawa, 1974). With a view to the grade of copper matte at a normal
level (45–65 wt.% Cu) in a majority of the matte smelting stages, copper
loss the slag mainly results from mechanical entrainment owing to the
elevated slag viscosity and increased melting point attributed to the
unavoidable formation of an excess of fine magnetite particles in the
copper slag (Kierczak et al., 2013; Muravyov et al., 2012). In the
H. Tian et al.
cleaning furnace process, in addition to the minimised slag layer,
increased temperature, and settling duration, improved recovery
methods are used, which can be mainly summarised as follows: (i)
reducing agents, such as pulverised carbon, heavy oil, and methane, and
vulcanising agent (FeS2) are commonly added to the copper slag to
weaken the surface tension and accelerate the mass transport between
the matte (or copper) and slag interface, by reducing Fe3O4 to FeO, and
subsequently generating Fe2SiO4 through a reaction with SiO2; (ii) cal­
cium oxide and alumina are added during the matte smelting stage to
stabilise the slag structure and balance the slag basicity, as well as
decrease the melting point and viscosity of the slag; (iii) an appropriate
amount of nitrogen is blown into the molten copper slag for increasing
the collision probability of copper drops, sequentially accelerating the
growth of fine copper drops, which results in an increase in their set­
tleability. The above-mentioned methods for treating copper smelting
slag decrease the copper loss of the copper pyrometallurgical process by
Fig. 1. Typical copper pyrometallurgical process and the main chemical reactions of the smelting stage.
3
Resources, Conservation & Recycling 168 (2021) 105366
improving the separation efficiency of the matte (or copper)/slag and
the sedimentation rate of the fine copper and matte droplets (Lu et al.,
2011; Gorai et al., 2003). The copper slag produced by the slag cleaning
furnaces as a final by-product, yields copper in the range of 0.55–1.3 wt.
% in the discarded slag, with copper losses of most plants in the dis­
carded slag limited between 0.8 wt.% and 1.0 wt.% (Coursol et al.,
2012). However, the final copper slag still contains large amounts of
valuable metals, such as Cu, Fe, Zn, Co, and Ni, and toxic elements
including Pb and As, which need to be subjected to further metallurgical
recycling and cleaning in consideration of economic performances and
environmental protections. It needs to be emphasised that the final
copper slag includes not only that dumped from cleaning the furnace,
but also the historical copper slag which may be traced back to several
decades.
H. Tian et al. Resources, Conservation & Recycling 168 (2021) 105366

3. Chemical and physical characteristics of copper slag
3.1. Chemical composition
Copper slag is mainly generated in the stages of matte smelting and
subsequent copper matte blowing; therefore the chemical composition
of copper slag samples varies significantly (Table 1), affected by the
type of smelting process, smelted ores, fluxes, and additives added
during the pyrometallurgical process (Lottermoser, 2005; Ettler and
Johan, 2014). In general, the prevailing elements contained in the waste
slag are Fe and Si. Other less prevalent elements include Cu, Zn, Ca, Mg,
and Al; and possibly Ni, Co, and Cr. Arsenic (As), a toxic element and Pb,
a heavy metal also exist in some copper slags. As shown in Table 1,
almost all the copper slags contain a considerable amount of Cu (0.5% –
2.7%) and Fe (31.7% – 40.3%), which come up to or even higher than
those of some general Cu and Fe ore mines. The grade of copper
generated from converter slag (slag 3) is commonly higher than that of
other copper slags, on account of the feed, i.e. copper matte, added into
the converter for blowing containing higher-grade copper. In addition,
some slags contain Zn, Ni, and/or Co at levels worthy of recycling.
Owing to the complicated occurrence of these elements, economic and
environmental treatment for different categories of copper slag should
be considered as comprehensively as possible.
(Mg2SiO4) and kirschsteinite (CaFeSiO4) are also often observed. Other
phases representing silicate-group minerals, such as hedenbergite (CaFe
(SiO3)2), diopside (CaMg(SiO3)2), essonite (Ca3Al2(SiO4)3) and
willemite (Zn2SiO4) are also commonly found in copper slag. In addi­
tion, an analysis of a copper slag showed a fairly common formation of
oxides, such as magnetite (Fe3O4), hematite (Fe2O3), copper dioxide
(CuO), zinc ferrite (ZnFe2O4), lead ferrite (PbFe2O4), and spinel
(MgAl2O4). Moreover, many elements (e.g. Cu, Fe, Zn, Pb, As, and Ni) in
the copper slag are predominantly associated with copper sulphides,
such as chalcocite (Cu2S), chalcopyrite (CuFeS2), and bornite (Cu5FeS4),
as well as other sulphide phases, such as pyrrhotite (Fe(1-x)S), sphalerite
((Zn, Fe)S), galena (PbS), arsenones (As2S3), and pentlandite ((Fe,
Ni)9S8), because these phases are often associated (or mutualistic) with
the copper mines. Additionally, with the effect of weathering, in some
copper slags, a number of different secondary phases are usually rep­
resented by carbonates, such as cerussite (PbCO3), conichalcite (CaCu
(AsO4)(OH)), hydrozincite (Zn5(CO3)2(OH)2), hydrocerussite
(Pb3(CO3)2(OH)2), and bayldonite (PbCu3(AsO4)2(OH)2). The genera­
tion of secondary phases is related to external factors (e.g. redox prop­
erty, pH), as well as the high-activity of other compounds and ions
accelerating the generation of these particular phases.
3.3. Physical properties

3.2. Phase composition The typical copper slag is generally black or dark brown in colour
and its density is in the range of 3.2 – 4.5 g/cm3, mainly depending on
The typical phase composition of copper slags is summarised in the content of Fe (Sarfo et al., 2017b). The average true density of
Table 2. Many variations in the phase composition of copper slags can copper slag is approximately 3.8 g/cm3, which is denser than the ordi­
be observed because of some factors related to the pyrometallurgical nary natural aggregates (Shi et al., 2008). In general, for a slow-cooled
process, such as characteristics of the copper mine processed, type of copper slag, it commonly presents the characteristics of dense, hard and
furnaces applied, type of additives (or flux) added, and type of cooling crystalline states, whereas a quenching treatment of slag results in a
methods adopted (cooling rate, cooling temperature ended, cooling glassy, granulated, and amorphous material; however, both of them are
medium), etc. (Lottermoser, 2002; Mateuset al., 2011; Gbor et al., hard, brittle, and difficult to grind . Furthermore, the slow-cooled copper
2000). For relevant pyrometallurgical processes for copper smelting, slag has a more unit weight and worse water absorption compared to a
these operating conditions may be diverse and consequently the phase quenching copper slag, owing to its less porous texture (Guo et al.,
composition in the copper slag may be different. Furthermore, weath­ 2017a). The characteristics of high stability and low conductivity are
ering may also affect the phase composition if the copper slag is also testified. Hence, we should take the physical properties of copper
deposited for a long time in a complicated environment (Mihailova and slags into full consideration, when they are handled by metallurgical
Mehandjiev, 2010; Piatak et al., 2015). Fayalite (Fe2SiO4) is the main recycling processes, or applied in civil material applications.
phase that volumetrically represents major compounds of the copper
slag. Addition to fayalite, olivine-group phases, such as forsterite
Table 2.
Table 1. Typical occurrence state of major elements in copper slag.
Typical chemical compositions of copper slag samples (wt.%).
Elements Phases Ref.
Element Slag 1 Slag 2 Slag 3 Slag 4 Slag 5 Slag 6 Slag 7
Cu Cu2S, Cu5FeS4, CuFeS2, CuO, Álvarez-Valero et al., 2009;
Cu 1.20 0.80 2.71 0.58 0.83 0.67 1.13 PbCu3(AsO4)2(OH)2 Kierczak et al., 2013
Fe 31.7 39.10 39.56 38.6 37.9 40.31 35.25 Fe Fe2SiO4, Fe3O4, Fe2O3, CaFeSiO4, CaFe Mihailova and Mehandjiev,
Si 16.48 14.52 12.42 14.33 16.33 11.84 15.01 (SiO3)2, Cu5FeS4, (Zn, Fe)S, Fe(1-x)S 2010; Mateus et al., 2011
Ca 0.51 1.74 1.79 1.20 1.43 8.35 8.84 Si SiO2, Mg2SiO4, CaMg(SiO3)2, CaSiO3, Vítková et al.; 2010; Mateus
Mg 0.14 1.07 0.63 1.16 0.90 0.49 1.73 Ca3Al2(SiO4)3 et al., 2011; Jiang et al.,
Al 2.05 1.21 1.96 1.83 2.44 2.06 2.39 2019
Zn 0.30 - 1.93 - 0.96 2.21 0.23 Ca CaFeSiO4, CaMg(SiO3)2, CaFe(SiO3)2, Mateus et al., 2011; Ettler
Pb 0.10 0.13 0.68 - 0.15 1.02 0.11 Ca3Al2(SiO4)3, CaCu(AsO4)(OH) et al., 2009; Jiang et al.,
As - - 0.043 - 0.14 - 0.36 2019
Ni - - 0.48 - - - 0,10 Mg Mg2SiO4, MgAl2O4 Manasse and Mellini, 2002;
Co - - - 0.21 - - 1.20 Vítková et al., 2010
Cr 0.05 - 0.04 0.57 0.05 - 0.75 Al MgAl2O4, Ca3Al2(SiO4)3 Lottermoser, 2002; Jiang
S 0.7 0.45 0.83 0.93 0.59 - - et al., 2019
Zn ZnFe2O4, (Zn, Fe)S, Zn2SiO4, Mateus et al., 2011; Á
Slag 1: Flash smelting slag from Almalyk copper-smelting plant, Uzbekistan
Zn5(CO3)2(OH)2 lvarez-Valero et al., 2009;
(Starodub et al., 2016); Slag 2: cleaning of electric furnace slag from Tongling Pb PbFe2O4, PbS, PbCO3, Ettler et al., 2009; Piatak
Non-ferrous Metals Group Holding Co., Ltd, China (Guo et al., 2016b); Slag 3: Pb3(CO3)2(OH)2, PbCu3(AsO4)2(OH)2 et al., 2015
Converter slag from Tongling Non-ferrous Metals Group Holding Co., Ltd, China As As2S3, FeAsO4•2H2O, Lottermoser, 2005; Piatak
(Guo et al., 2018a); Slag 4: Slow-cooled slag from INCO’s flash smelting furnace PbCu3(AsO4)2(OH)2, CaCu(AsO4)(OH) et al., 2015
in Sudbury, Ontario, Canada (Gbor et al., 2000); Slag 5: Water quenched of Flash Ni (Fe,Ni)9S8 Vítková et al., 2010;
furnace copper slag from the of a copper smelter, Japan (Fan et al., 2015); Slag 6: Co CoO, CoS Panda et al., 2015
Reverberatory furnace slag from copper-smelting plant, Italy (Manasse et al., Cr Mg(Al, Cr)O4 Vítková et al., 2010
S Cu2S, Cu5FeS4, CuFeS2, FeS, (Zn, Fe)S, Lottermoser, 2011; Piatak
2001); 7: Blast furnace slag from copper-smelting plant, Zambia (Vítková et al.,
PbS, (Fe, Ni)9S8 et al., 2015
2010). “-”: not reported.

4
H. Tian et al.
3.4. Microstructure morphology
Fig. 2 shows the typical microstructure of a copper slag sample,
which presents that fayalite is the dominant phase in the copper slag,
and it is tightly combined with the magnetite and copper matte.
Furthermore, the matte and metallic Cu, which are the copper-bearing
phases that are originated from mechanical entrainment and entrap­
ping into a slag during the process of matte-slag separation; and the
magnetite are characterised by ultrafine grained sizes of a few microns,
dispersed in the slag. The particle dimension of the copper matte is in the
range of 10 – 20 μm, and that of the metallic copper is much tinier (less
than 5 μm). In addition, some metal-oxygen and metal-sulphur struc­
tural phases may also appear, as illustrated by matching metal and ox­
ygen (sulphur) distribution arrangement, shown in Fig. 3. This figure
shows the elemental distribution image of Fe, O, Si, Cu, S, and Zn.
Furthermore, lead sulphide presents itself along with zinc embedded
into the magnetite and copper matte, and its particle dimension is less
than 5 μm. Therefore, the characteristics of relatively super micro-
grained dissemination and maldistribution of valuable and harmful el­
ements in the copper slag will pose challenges to its economic and
environmental treatment.
3.5. Thermal properties
Fig. 4 shows the thermogravimetric analysis (TG) and differential
thermal analysis (DTA) profile of a copper slag sample under air atmo­
sphere to reveal its thermal stability. According to the diagram, the TG-
DTA results demonstrate a steadily increasing weight until 1180 ◦ C,
whereof it appears to slow down and then flatten. The weight increment
is attributed to the oxidation of both Fe2SiO4 (at approximately 750 ◦ C)
and Fe3O4 (at approximately 400 ◦ C) to Fe2O3. The relevant oxidation
reactions are listed in Eqs. (1) and (2). Moreover, Fe/Cu sulphides
existing in the copper slag can be transformed into corresponding oxides
(at approximately 1000 ◦ C) as illustrated in Eq. (3). A study on the
thermal transformation of phases can reveal the beneficial effect of
subsequent treatments.
2Fe2SiO4 + O2 = 2Fe2O3 + 2SiO2 (1)
4Fe3O4 + O2 = 6Fe2O3 (2)
MxSy + (x + y)O2 = xMO2 + ySO2 (3)
4. Metallurgical recycling and cleaning of copper slag
4.1. Flotation
Flotation is an effective physical beneficiation for the recovery of
copper in metallic and sulphide states entrapped in a copper slag by fine
grinding, and addition of one or more corresponding flotation reagents,
Fig. 2. Typical microstructure of a copper slag through by slowly cooled (Guo et al., 2016).
5
Resources, Conservation & Recycling 168 (2021) 105366
such as a collector, frother, depressant, pH regulator, dispersant, floc­
culant, or vulcanising agent. The choice of the reagent depends on the
floatability and the difference in the surface hydrophilicity of the slag
phase compared to those of the other phases (Zhai et al., 2019; Hu et al.,
2011). In general, high-grade copper concentrates can be obtained
through the treatment of copper slag by the flotation process, which
includes coarse crushing, fine grinding, size grading, mineral/reagent
mixing, select flotation, and dehydration. The typical flow process dia­
gram of floatation is illustrated in Fig. 5. The efficiency of flotation is
affected by various parameters, such as the cooling schedule of the
molten copper slag, slag composition, fine particle size fraction, pulp
pH, flotation time, solid content of the pulp, and the amount and type of
flotation reagents. A summary of the results from the aforementioned
studies is displayed in Table 3.
Based on the differences in the cooling schedule, copper slags can be
divided into slow cooling, air cooling, and water-quenched slags (Guo
et al., 2017a). Generally, slow cooling slags are more beneficial for
better recovery of copper by flotation. A slow cooling rate of the molten
copper slag can minimise the effect of viscosity on the mass transfer of
diffusion and grain growth of matte copper (or metallic copper), and
further help in the subsequent fine grinding and flotation stages of
copper recovery. In comparison, a fast cooling rate generates fine par­
ticles of matte copper (or metallic copper), and an amorphous fine
grained structure, which adversely affects the degree of liberation or
separation from the gangue minerals during the grinding process, as well
as the flotation efficiency (Sarfo et al., 2017a; Guo et al., 2018c; Panda
et al., 2015). In a study, when the cooling rate of a molten copper slag
was controlled below 3 ◦ C/min, the particle size of the copper matte
reached up to 97% larger than 10 μm. On the other hand, it was only 6%
larger than 10 μm under water-quenched treatment (Guo et al., 2018c;
Rozendaal and Horn, 2013). It should to be emphasised that when the
temperature was below the liquidus temperature (TLiquidus), the cooling
rate of the molten copper slag would not significantly affect the crys­
tallisation behaviour of the copper matte (or metallic copper). There­
fore, slow cooling with 1–3 ◦ C/min of the molten copper slag in the
cinder ladle down to nearly 1000 ◦ C, followed by water-quenched
treatment can, not only obtain a favourable flotation efficiency, but
also shorten the cooling time. Simultaneously it can recover a sensible
heat of approximately 1000 MJ (equivalent of 34 Kg of standard coal)
per ton of the molten copper slag, thus decreasing its temperature from
1200 to 1000 ◦ C (Guo et al., 2017b). Furthermore, the slow cooling
slag-entrained copper matte (or metallic copper) in fayalite (iron-­
silicate) matrix should be ground finely at least below 45 µm to meet the
requirements of the subsequent flotation (Roy et al., 2015). The
closed-circuit flotation flowchart typically includes roughing, scav­
enging, and cleaning stages, each performed one or more times. The
concentrates of the scavenging and the tailings of the cleaning need to
return to a rougher cell for decreasing the loss of copper (Yuan et al.,
2019; Guo, 2019). According to the characteristics of a ground copper
slag sample, the selection of flotation reagents can be diverse and each of
H. Tian et al. Resources, Conservation & Recycling 168 (2021) 105366

Fig. 3. Scanning electron micrograph and elemental distribution image of a copper slag (Chun et al., 2016; Zuo et al., 2019) (A – Fe2SiO4, B – Cu2S•FeS, C – ZnS, M –
Fe3O4, and G – Glassy substance).

Fig. 4. TG-DTA profile of copper slag (Sarfo et al., 2017b).

6
H. Tian et al.
Fig. 5. Flowchart of flotation process for the recovery of copper from copper slag (inset diagram shows the effect of cooling rate of molten slag on the flotation
efficiency) (Sarrafi et al., 2004).
them has relative specificity. The collectors, which are one of the most
important flotation reagents used for selectively adsorbing on copper
matte (or metallic copper) surfaces, and increasing the hydrophobic
character to make them adhere to the bubbles for improving the float­
ability, typically include sodium sec-butyl xanthate, potassium amyl
xanthate, and alkyl hydroxamate. In addition, some flotation effects
were improved obviously by a mixture of collectors because of the
competitive adsorption; for example, a improved copper recovery
(84.82%) can be obtained when a 40:160 g/t mixture of sodium
iso-propyl xanthate (SIPX) and di-ethyldithiophosphate (DTP) was used
compared to 78.11%, obtained with the best single collector (Roy et al.,
2015; Shi et al., 2019; Kong et al. 2015;). In addition, frothers such as
methyl isobutyl carbinol (MIBC) and pine oil are used to (i) decrease the
surface tension of water to form bubbles, and (ii) promote absorption on
the surfaces of selectively floated copper matte (or metallic copper) to
improve the floatation efficiency (Bruckard et al., 2004; Sarrafi et al.,
2004). Furthermore, the hydroxy ethyl cellulose as a depressant of
magnetite and calcium oxide as a pH regulator are also applied to
improve the copper grade of concentrates, and adjust the surface hy­
drophilicity of the copper matte (or metallic copper), as well as the
dissociation of effective ions from flotation reagents, respectively. Cal­
cium oxide is also a flocculant, which can accelerate the condensation of
fine grain in ore pulp and sedimentation of tailings (Lai et al., 2017; Sun
et al., 2019).
The flotation of copper slag can effectively recover copper, without
recycling other valuable metals in the copper slag. However, this process
requires a much higher water content and offers relatively low envi­
ronmental benefits. Moreover, large areas are occupied by cinder ladles
in this process, and a long time is required for slow cooling the copper
slag, resulting in a high cost of land and low production efficiency.
7
Resources, Conservation & Recycling 168 (2021) 105366
4.2. Leaching
Leaching is a significant method for recycling valuable metals and
refining copper slag, and achieves the desired results through reactions
between the valuable (or harmful) metal elements in the slag and some
chemical leaching agents or biotic solutions added to the slag, followed
by subsequent filtration, washing, and extraction (Georgiev et al., 2017;
Baghalha et al., 2007). Depending on the reactions of the method and
the medium, the leaching process for copper slag can be grouped into
two main types, chemical leaching (e.g. acid leaching and alkaline
leaching), and bioleaching, which has also caught much attention in
recent decades because of its preferable adaptability and sustainability
for recycling valuable elements from copper slag (Potysz et al., 2015;
Lee and Pandey, 2012). Key results from these studies are summarised in
Table 4. Finally, solutions with considerable concentrations of valuable
elements can be obtained by an effective leaching process.
4.2.1. Chemical leaching
The chemical or acid leaching process is mainly divided into atmo­
spheric pressure acid leaching and high-pressure oxidative acid leach­
ing. The atmospheric pressure acid leaching is a traditional approach for
recycling metals of copper slag. It is characterised by a compact process
flow route, low investment, and maintenance cost (Yang et al., 2010).
The leaching agents typically include H2SO4, HNO3, and HCl. Of these,
H2SO4 is considered as the best choice for leaching metals owing to its
low price for similar solubility level of metal elements. Generally, with
H2SO4 as a leaching agent, the leaching efficiencies of different metal
elements from the copper slag vary notably, depending on the corre­
sponding leaching factors, mainly consisting of acid concentration, liq­
uid/slag ratio, processing time, leaching temperature, particle size, and
H. Tian et al. Resources, Conservation & Recycling 168 (2021) 105366

Table 3. Table 4.
Flotation efficiency for the recovery of copper from copper slag. (Bio)leaching efficiency for the recycling treatment of valuable metals from
Cu grade Flotation Flotation Flotation efficiency Ref.
copper slag.
of conditions reagents, (wt.%) Chemical (Bio)leaching (Bio)leaching (Bio) Ref.
copper dosage (g/t) Grade Recovery composition agents (culture) parameters leaching
slag (wt. and mixing (wt.%) efficiency
%) time(min) (wt.%)
1.9 One roughing, 80% Collector: 17.86 83.07 Roy Cu-converter H2SO4 PZ of less than 92% of Cu, Anand
passing size of 75 mixture of et al., slag 270 µm, acid 95% of Ni et al.,
μm, 9 of pH, 1000 SIPX and DTP, 2015 Fe: 38.32%, concentration of and 95% of 1983
rpm of stirring rate 200(40:160), Cu: 4.03%, 0.35 mol/L, Co
for 13 min and 7 L/ 6 Co:0.49%, oxygen pressure
min of air flow rate Frother: pine Ni: 1.97% of 0.59Mpa, SR/
oil, 100, 1 LR of 10%, AS of
pH regulator: 840 rpm, LTM of
NaOH, NR*, 6 130 ◦ C and LTE
1.9 One roughing, 80% Collector: 17.41 78.11 Roy of 4h.
passing size of 75 SIPX, 200, 6 et al., Cu-smelter H2SO4 and H2O2 PZ of less than 80% of Cu, Banza
μm, 9 of pH, 1000 Frother: pine 2015 slag 100 µm, pH of 90% of Co, et al.,
rpm of stirring rate oil, 100, 1 Fe(II): 2.5, H2O2 of 62.5 90% of Zn 2002
for 13 min and 7 L/ pH regulator: 20.7%, Cu: L/t slag, LR/SR and 5% of
min of air flow rate NaOH, NR, 6 1.43%, Zn: of 10, Eh of 650 Fe
1.83 Two roughings, Collector: 28.84 87.59 Sun 8.9%, Co: mV, LTM of 70
67% of slurry BK901B, 20, 2 et al., 0.72% ◦
C and LTE of 1
concentration, 90% Frother: pine 2019 h.
passing size of oil, 20, 2 Cu-converter H2SO4 and H2O PZ of less than 93% of Cu Deng
43μm and 7.5 of pH Vulcanized slag 270 µm, S/L and 98% of and
agent: Na2S, Fe: 51.04%, during ageing of Co Ling,
500, 3 Cu: 2.33%, 50% (H2SO4), 2007
1.42 One roughing and Collector: 7.2 66.95 Zhai Co: 0.44% LTM of 250 ◦ C,
one scavenging, Butyl et al., LT of 15 days;
4–5 min of xanthate, 2019 SR/LR during
floatation time, 50–100, 3 leaching of 20%
95% passing size of Frother: (H2O), AS of
45 μm and 7 of pH Terpineol, 30- 200rpm, LTM of
50, 3 80 ◦ C, LTE of 1h.
0.67 Two roughings, Collector: 18.04 88.68 Yuan Cu-converter (NH4)2SO4 and PZ of less than 85% of Cu, Sukla
two scavengings Butyl et al., slag H2O 75 µm, roasting 85% of Co, et al.,
and two cleanings, xanthate, 2019 Fe: 38.32%, with (NH4)2SO4 80% of Ni 1986
3–8 min of 20–30, 3 Cu: 4.03%, of 2.5 and 37% of
floatation time, Frother: pine Co:0.48%, stoichiometric at Fe
90% passing size of oil, 10–20, 1 Ni: 1.98% LTM of 400◦ C
45 μm and 7.5 of pH regulator: and LTE of 1 h
pH CaCO3 and followed by
Na2CO3, NR, water leaching
NR Cu-smelter (NH4)2SO4 PZ of less than 75% of Cu Roy
Vulcanized slag 42 µm, 0.96 et al.,
agent: Na2S, Fe: 47.94%, mol/L of 2016
250, 5 Cu: 0.74% ammonia
concentration,
pH of 8.5-10.8,
oxygen delivery. (Baghalha et al., 2007; Altundogan et al., 2004). Most SR/LR of 10%,
research experiments on this subject showed a relatively close relevance AS of 500 rpm,
LTM of 45 ◦ C
between the leaching performance and acid concentration, implying
and LTE of 4h.
that the increase of acidity can enhance extraction of valuable elements Cu-converter Aspergillus niger PZ of less than 78.5% of Sukla
to a significant extent. (Anand et al., 1983;). However, the excessive slag 150 µm, pH of Cu, 90% of et al.,
acidity may present an adverse effect on the leaching process because of Fe: 38.82%, 6.8, LR/SR of 50, Co, 45.5% 1995
the generation of silica gel (SiO2∙2H2O) (Eq. (4)), which would make Cu: 4.03%, AS of 120 rpm, of Ni and
Co: 0.48%, LTM of 37◦ C, 40.15% of
the leach liquor more viscous, causing problems for pulp filtration and Ni: 1.98% LTE of 72 h in Fe
subsequent operations (Yang et al., 2010; Huang et al., 2012). Moreover, potato dextrose
the existence of high fayalite content in the copper slag also generated a medium.
negative effect on the cost-efficient process owing to the high levels of Cu-smelter Acidithiobacillus pH of 0.5-1.0, 100% of Vestola
slag and LR/SR of 99, Cu, 100% et al.,
acid and extraction agent consumption during the recycling process.
Fe: 40.7%, Leptospirillum supplemented of Ni and 2010
Seen from this perspective, the dissolution of iron in the leaching solu­ Cu: 0.35%, with 1% S0, AS 64% of Zn
tion are identified as a burden against the leaching and subsequent Zn: 1.7%, of 500 rpm, LTM
extraction processes (Ahmed et al., 2012; Zhang et al., 2019a). Ni: 0.19% of 22 ◦ C, LTE of
79days in
2MO⋅SiO2 + H2 SO4 →2MSO4 + SiO2 ⋅2H2 O (M : Fe, Zn, Mg, Ca, etc.) (4) mineral salt
medium.
To address the above problems, H2O2 as an oxidant was used to *
greatly decrease the content of silica gel and the dissolution of iron Roy PZ: Particle size, SR/LR: solid-liquid ratio, LR/SR: liquid-solid ratio, AS:
agitation speed, LTE: leaching time, LTM: leaching temperature
et al., 2016; Li et al., 2019c). Here, leaching of fayalite by sulphuric acid
generates Fe2+, which is oxidised to Fe3+, causing the precipitation of Fe
(OH)3 and FeOOH by suitable addition of H2O2, as indicated in Eqs. (5)
and ((6). Therefore, the application of oxidant is beneficial to not only

8
H. Tian et al.
eliminate the negative influence of silica gel, but also remove the iron
out of the leachate as its oxidative precipitation, as shown in Eq. (7).
Furthermore, some experiment studies also disclosed the important of
oxidizing conditions for improving the extraction of valuable metals,
through an increase in the Eh values (Qi et al., 2012; Sun et al., 2017).
2FeSO4 + H2 O2 + 2H2 O→2FeOOH + 2H2 SO4 (5)
2CuFeS2 + 2H2 SO4 + 5H2 O2 →2CuSO4 + 2Fe(OH)3 + 4H2 O + 4S (6)
2MS + 7H2 SO4 + H2 O2 →2MSO4 + 7H2 SO3 + H2 O (M
: Cu, Fe, Co, Zn, Pb, As, etc.) (7)
Further research indicated that, in addition to higher acid concen­
tration and oxygenated conditions, elevated temperature, smaller sizes,
diluted pulp density, and also yielded preferable leaching performances.
The temperature affects the metal leaching rate by changing the kinetics
of reaction, and improves both the metal leachability and the leaching
efficiency. Temperatures range between 24–100 ◦ C for high-tempera­
ture leaching (Carranza et al., 2009a); 20–250 ◦ C for strengthening
leaching with heat aging treatment (Deng and Ling, 2007); and 30–800
◦
C for slag roasting with vulcanising agents (e.g. H2S, H2SO4, Fe2(S­
O4)3•xH2O, and FeS2), following acid or water leaching (Rashid et al.,
2019; Li et al., 2019a; Nadirovel al., 2013; Sun et al., 2017). However,
the thermal activation of copper slag was proved to be a catalysing factor
only until a certain temperature because of the evaporation of acid
leachates at excessive temperatures. Furthermore, the optimum value of
pulp density and size are beneficial to the contact of the leachate with
the metal-bearing mineral particles in the copper slag (Altundoğan and
Boyrazli, 2004).
As mentioned above, in atmospheric pressure acid leaching of copper
slag, unavoidable inclusion of Fe (Mg, Ca)-bearing compounds into
leachate can result in extra consumption of leaching agents and oxi­
dants, as well as a long leaching duration. This imposes a serious limi­
tation on the economic benefits of this process (Li et al., 2009; Li et al.,
2008). Hence, a high-pressure oxidative acid leaching process (HPAL) at
elevated temperatures was proposed to avoid high acid consumption
and long leaching durations for the treatment of copper slag. This pro­
cess characterised by high leaching rate and low acid consumption could
finish the recycling of target elements into leachate in 25–45 min at
200–300 ◦ C. Compared to the atmospheric pressure acid leaching with
acid addition of minimum of 175 wt.% of slag weight, less quantity of
H2SO4 with only 20 wt.% is required in the HPAL through regeneration
of acid medium (Banza et al., 2002). The HPAL was successfully
employed to treatment the retarded cooling Cu-slag containing 4.0% Cu,
0.5% Co, and 2.0% Ni in Canada. The recovery of Ni, Co, and Cu can
reach above 90% and 97% within 20 min and 45 min, respectively, at
250 ◦ C, 70 g/L of initial H2SO4, and 90 psi of O2 overpressure, while the
extraction of Fe was only as low as 0.8% (Anand et al., 1983). However,
in addition to the consumption of H2SO4, the operating costs during the
HPAL should also be taken into economic consideration. For example,
the operating conditions of 250 ◦ C may also require the recovery of
waste heat through multi-stage vapor circulation to decrease the addi­
tional source of heat (Perederiy et al., 2011). To sum up, the
above-mentioned measures and improvement are aimed to establish a
high-efficiency and cost-effective acid leaching process.
As acid leaching applied to the treatment of copper slags still has
many limitations to some extent, ammonia leaching, as an alkali
leaching process, gradually become one of the alternative options
because of its preferable intrinsic advantages such as low corrosiveness
of ammonia leaching solution to equipment system, and favourable se­
lective leaching of the valuable metals (Bidari and Aghazadeh, 2015).
During the ammonia leaching process, Cu, Co and Ni will be converted
into corresponding soluble ammine complexes and then migrate into
filter liquor for recycling, while Fe will be removed as insoluble oxy/­
hydroxyl compounds and still remain in the filter residue. (Nadirov et al,
9
Resources, Conservation & Recycling 168 (2021) 105366
2013).
The study on the selective recycling of copper from copper slag has
been paid relatively significant attention, which indicates that the
relative concentration of ammonia, pH of the leaching system, rate of
agitation, and size of particles, are principal elements to influence the
dissolvability of copper-bearing phases existed in the slag (Roy et al.,
2016; Nadirov et al, 2013). Research from most experiments indicates
that the pH value of the slurry plays a vital role in copper extraction,
which effects the formation of stable copper complexes, i.e. Cu (NH3)2+ 4 .
At an appropriate pH value range of the slurry, the copper-bearing
phases react readily with aqueous ammonia and ammonium sulphate
(or ammonium carbonate) supplemented by enough oxygen. The
appropriate Eh–pH condition at a range of 8.5 to 10.8 is essential to form
the phase of Cu (NH3)2+4 . The effect of pH on ammonia leaching effi­
ciency for copper extraction from copper slag is illustrated in Fig. 6. It
can be seen that the copper extraction showed a significantly increase
tendency because of the formation of Cu (NH3)2+ 4 with maintaining a
suitable range of pH. Therefore, controlling the pH of the leaching me­
dium by adding a little dilute sulphuric acid into the slurry was a good
strategy.
Furthermore, the rate of agitation has a noticeable influence on the
dissolution of copper-bearing phases. An elevated rate of agitation can
accelerate the abrasion of targeted phases and then expose fresh surface
sites to decrease the activation energy of ammonia leaching for further
reaction. What’s more, the encouraging effect of particle size of the
ground copper slag was observed only at a size below 42 µm, resulting in
a high degree of dissolution of copper because of the preferable degree of
dissociation separated from the gangue minerals (Potysz et al., 2015). In
the best performance, over 75% of copper could be recycled at 1.0 mol/L
of ammonia concentration, 10% of solids, 500 rpm of agitation rate and
less than 42 µm of particle size (Roy et al., 2016). However, the
ammoniacal leaching of copper slag, characterised by a complex
mineralogical composition also has some disadvantages, such as a large
loss of volatilisation and low environmental benefit. It is not suitable for
the recovery of iron from the view point of economy of the operation and
therefore, needs considerable amount of further research.
Combined with the relative merits of chemical leaching for the
treatment of copper slag, the disposal of leaching slag with a low uti­
lisation rate is a non-negligible factor for the environmental and eco­
nomic benefits of the leaching process. Based on the background, a
combinative residue-free leaching process for copper slag with sorting,
roasting, acid leaching, carbonate precipitation, ammonia leaching, and
solvent extraction steps was developed. The recycling route and material
balance of the developed leaching process illustrated in Fig. 7 shows
that four products can be obtained, namely abrasive blasting agent
(Product 1), cement additive (Product 2), valuable metal salts (Product
3), and NH4Cl/MgCl2 fertiliser (Product 4) (Miganei et al., 2017). As
shown in Fig. 8, on the basis of the type of cooling, the copper slag can be
classified into vitreous and crystalline types, suggesting two possible
routes for further treatment. The vitreous type was disposed by a stage
by stage crushing, combined with classification to obtain a size fraction
of particles between 0.2 and 2 mm for the production of abrasive
blasting materials. These materials can be applied into the field of ma­
terial surface processing (Biswas and Satapathy, 2010). The finer grain
fraction below 0.2 mm can be separated and mixed with the crystalline
type slag to take part in a subsequent process to ensure the recycling of
residue-free slag. Mixtures were crushed to below 2 mm and charged
into furnace at 800 ◦ C for oxidizing roasting so that the metallic sulphide
was oxidised. Depending on the study of reaction kinetics leaching, the
efficiency of selective metal leaching was the highest at an optimal pH of
approximately 2.5 at 70 ◦ C, a slurry density of 50%, and HCl concen­
tration of 37%. With the addition of NH4HCO3, partly dissolved calcium
was recovered in the form of CaCO3 and Fe was recovered as hydroxides
(Kim and Hong et al., 2004). The collective precipitation products were
reunited with the siliceous residue, and used as a cement additive after
H. Tian et al.
Fig. 6. Effect of pH on ammonia leaching efficiency for copper extraction from copper slag (Roy et al., 2016; Zhang et al., 2019a).
leaching of the metals. The sedimented metal carbonates were further
complexed as metal amines by the addition of NH4OH, and then stripped
as sulphates after a specific solvent extraction with H2SO4. The valuable
metal sulphate solutions will be superior raw materials for the produc­
tion of electrolytic metals. Furthermore, to meet the residue-free re­
quirements of the processing of copper slag, the precipitate-containing
chloride from HCl can be converted into a special NH4Cl-MgCl2 dual salt
fertiliser by the addition of NH4HCO3, and further crystallisation (Ash­
raf et al., 2005). Thus, the combinative residue-free leaching process
provided a novel method to recycle copper slag with more economic and
environmental benefits.
From the above studies it is understood that experimental methods of
chemical leaching have demonstrated the feasibility of dissolving sig­
nificant valuable metals existed in copper slag. Consequently, solutions
containing target metals in high concentration can be obtained through
effective chemical leaching (Kaksonen et al., 2011). Furthermore, it
should be emphasized that further treatments are required to separate
the dissolved metals from the solution for the successful accomplish­
ment of the recycling process. This last step of the process can be con­
ducted by solvent extraction or electrolytic deposition (Kordosky,
1992). Based on the above review and analysis, although chemical
leaching methods of recycling target metals from copper slag have been
already great established, optimising the parameters and improving the
technology for further recycling efficiency are still a significant research
challenge.
4.2.2. Bioleaching
Bioleaching has gradually become a viable alternative for conven­
tional chemical leaching to realise metallurgical recycling from copper
slags, and depends on the application of biotic solutions instead of
10
Resources, Conservation & Recycling 168 (2021) 105366
chemicals for metal solubilisation. Bioleaching is characterised by low
environmental pollution and costs, as well as a high metallic leaching
rate (Vestola et al., 2010; Bosecker et al., 1997). For that reason,
numerous laboratory investigations have been conducted to employ
bioleaching technology for the extraction of valuable metals from cop­
per slags. Biochemical interactions between microbial organisms and
copper slag have also been studied. Experiments have demonstrated that
the utilization of microorganisms into leaching process can achieve the
desired effects, obtaining an extraction efficiency of above 90% for Cu.
Besides, Co, Ni, and Zn, if present in the initial copper slag, may be also
simultaneously extracted. (Sukla et al., 1995)
In general, the utilisation of microbial ability is a substantial
contribution for bioleaching (Brandl & Faramarzi, 2006; Kaksonen et al.,
2011). Some bacteria and fungi as major used microbial organisms can
leach metals (Lee and Pandey, 2012; Muravyov and Formchenko, 2013).
Typical bacteria used for bioleaching are acidophilic bacteria mainly
containing acidithiobacillus ferrooxidans and acidithiobacillus thioox­
idans (Suzuki, 2001; Lee and Pandey, 2012). In addition, Aspergillus
niger, a type of fungus, was also applied to the bioleaching of
Cu-converter slag for efficiently leaching metal residues (Sukla et al.
1992). Acidophilic microbial organisms are tolerant of the environments
with a pH of even 0.7 because of the characteristics of high acid resis­
tance, which makes them especially relevant for bioleaching (Erüst
et al., 2013; Watling, 2006). Additionally, all of them can oxidise the
sulphide to the form of sulfate radical, while some acidophilic bacteria
are also capable of oxidising Fe2+ to Fe3+. Efficient dissolution of metals
using acidophilic microorganisms mainly depends on the control of pH
conditions (Suzuki, 2001; Watling, 2006). The optimum pH range for
the growth conditions of acidophilic microbial organisms is between1.5
and 2.5 to generate the essential Fe3+ to serve as an indirect leaching
H. Tian et al. Resources, Conservation & Recycling 168 (2021) 105366

Fig. 7. Flowchart of the combinative residue-free leaching process for copper slag recycling with the material balance (Miganei et al., 2017).

Fig. 8. Reaction mechanism and microstructure change of bioleaching for the treatment of copper slag (Bioleached by A. thiooxidans under a pulp density of 1%, pH
of 0.9, and treatment time of 21 d) (Potysz and Kierczak, 2019; Panda et al., 2015).

reagent, while the bacteria themselves play a direct role. Therefore, the microbiological leaching, which are illustrated in Fig. 8. The direct ef­
contribution of microbial organisms to metal extraction can be distin­ fect of acidophilic bacteria mainly reflects in the oxidation and solubi­
guished into two types of interactions, direct and indirect lisation of sulphide to build the condition of elevated acid concentration

11
H. Tian et al.
for improving the leaching performances. While for the indirect reac­
tion, acidophilic bacteria can realise the regeneration of Fe3+ by oxi­
dising Fe2+. Both reactions contribute to the dissolution of fayalite,
metallic copper, and copper sulphide (Mehta et al., 1999; Tuovin et al.,
2012; Muravyov et al., 2012). According to scanning electron micro­
scope observations, fayalite and copper-bearing phases show more
complete dissolution when exposed to acidophilic bacteria (Fig. 8C, D)
as compared to that in the absence of bioleaching (Fig. 8A, B).
Furthermore, it is worth mentioning that there are often some acid
insoluble minerals contained in the copper slag. With regard to the acid
insoluble minerals subjected to bioleaching, the indirect impact of mi­
croorganisms is deemed to be significant for the metallurgical recycling
in the leaching process (Tuovin et al., 2012; Kaksonen et al., 2011). The
redox potential determined by the oxidation of Fe2+ to Fe3+ is an
important factor affecting the leaching efficiency, which effects the
leaching rate because of the regeneration of the oxidant (Fe3+) will in­
crease the redox potential in the bioleaching solution. Hence, the bio­
leaching of copper slag can achieve the maximum efficiency at an
optimum redox potential and pH of leaching system.
Fig. 9. Typical flow process diagram of metallurgical recycling for copper slag through reduction roasting followed by magnetite separation, and the related
reduction behaviour of copper slag pellets (Li et al., 2019b; Guo et al., 2017a).
12
Resources, Conservation & Recycling 168 (2021) 105366
Therefore, controlling the pH of 1-2 during bioleaching is essential
for the regeneration of ferric iron and acid by microbial organisms. In
addition to maintaining the suitable pH, some other experimental con­
ditions can also affect the efficiency of the bioleaching process. For
instance, combination of different microorganism, such as some auto­
trophic and heterotrophic bacteria, is demonstrated to be beneficial for
the process of sulphide mineral leaching (Lee and Pandey, 2012;
Bosecker, 1997). Moreover, the application of thermoacidophile can
further improve the bioleaching efficiency depending on their heat
resisting property under high acidic conditions (Tuovinen et al., 2012).
Therefore, the elevated temperature during the bioleaching process
contributes to obtaining a higher dissolution velocity and less leaching
time. It is worth noting that an appropriate pulp density in the bio­
leaching tests can also bring positive influence on the leaching efficiency
ranging from 7%–10% (weight/volume) (Sukla et al., 1995).
4.3. Reduction roasting followed by magnetic separation
Reduction roasting followed by magnetic separation has been
H. Tian et al.
regarded as an effective route to realise metallurgical recycling, e.g.
recovery of Cu, Fe, Zn, and Pb from copper slag. This process promotes
the reduction of metal-bearing phases and the increase in size of iron-
based fine grains (Guo et al., 2018a; Liu et al., 2019a). In general,
reduction roasting followed by magnetic separation for the metallur­
gical recycling of copper slag can be subdivided into several workstages,
namely crushing, sieving, proportioning, blending, pelletising, and
reduction roasting, followed by magnetic separation or dust-collection
to obtain Fe-Cu concentrates, as well as dust-containing Zn and Pb, if
present in the initial copper slag. A typical flow process diagram of
reduction roasting followed by magnetic separation is illustrated in
Fig. 9. Generally, the carbothermic reduction roasting is the primary
procedure for the treatment of copper slag. Over the last few decades,
many studies were conducted to reveal the reduction behaviours of
metal oxides and sulphides in the copper slag by various reductants. The
reductants fall into two major types, namely solid reductive agents
(bitumite, anthracite, graphite, and coke) (Wang et al., 2018; Zhang
et al., 2015; Zhang et al, 2013), and gaseous reductive agents (H2, CO,
CH4, and natural gas) (Seo et al., 2000; Utigard et al., 1997; Nagasaka
et al., 2000). According to the previously reported literature, CO is
generated via Boudouard reaction (CO2+C=2CO), when solid reductant
is employed as the main reductant in reduction roasting process (Siwiec
et al., 2014; Tian et al., 2020). As mentioned in section 3.2, Fe (Cu, Zn,
Pb)-bearing phases include Fe2O3, Fe3O4, Fe2SiO4, Cu2S, CuO, ZnS,
ZnFe2O4, ZnO, PbS, PbFe2O4, and PbO. With a CO atmosphere and the
corresponding reactive temperature, the reduction of metallic oxides is
commonly conducted step-by-step as Fe2O3 → Fe3O4 → FeO → Fe; CuO
→ Cu; ZnFe2O4 → ZnO → Zn; and PbFe2O4 → PbO → Pb, while Fe2SiO4,
Cu2S, ZnS, and PbS are difficult to reduce into metallic states without the
additives added, which affects the recycling efficiency from copper slag
(Li et al., 2019b; Guo et al., 2018a). Based on the above reasons, CaO as
an additive is used to accelerate the phase transformation as Fe2SiO4 →
FeO → Fe, which is beneficial to the increase of metallisation rate and
recycling of iron. Furthermore, CaO can also react with Cu2S, ZnS, and
PbS to accelerate the reduction of sulphides, sequentially increasing the
metallisation rate and recycling of copper, zinc, and lead. This is also
indicated in Fig. 9.
Furthermore, in carbothermic reduction roasting of copper slag,
silicates and iron oxide are the main and typical phases in the copper
slags, resulting in an iron-based alloy as reduced metallic phase (Liu
et al., 2019a; Zhang et al., 2013). Simultaneously, metallic copper will
also be dissolved into the iron-based alloy (metal phase), which is
generated from the reduction of copper oxides (or sulphides). Copper is
commonly soluble with iron because of the good affinity with each other
at a suitable temperature and range of composition (Wang et al., 2019;
Yao et al., 2019). Although the existence of copper will go against the
quality of pig iron, some antifriction alloys containing considerable
quantity of copper (Cu <1.5%) are applied into production, and can also
be acceptable in weather-resistant steel (Cu 1–2%). It is also adopted to
match iron-based alloy with other pig iron to satisfy the qualification. In
practice, the copper grade of an iron-rich alloy is generally determined
by not only the copper and iron percentages in the initial slag, prior to
the carbothermic reduction, but also the carburisation of the alloy owing
to excessive reducing agents. In other words, carbon, typically saturated
in a molten iron-based alloy, can decrease the solubility of copper to
some extent, which can be indicated by thermodynamic calculations of
Fe-Cu-C ternary phase equilibrium systems (Sarfo et al., 2017b). Now
that the copper presented in the copper slag will inevitably associate
itself with the iron-based alloy, the effect of carbon content on the sol­
ubility of copper in iron-based alloy becomes effective and significant.
Therefore, the utilisation range of the iron-rich alloy can be also further
enlarged by an adjustment of the copper content, depending on the
carburisation during the reduction of copper slag (Sarfo et al., 2017b;
Wang et al., 2018). In addition to the iron-based alloy, which can be
extracted by multiple-stage fine grinding and magnetic separation, other
metallic elements (e.g. Zn and Pb), if present as the form of Zn-bearing or
13
Resources, Conservation & Recycling 168 (2021) 105366
Pb-bearing phases in the copper slag, will also change to the corre­
sponding simple substances, and then will mostly evaporate at an
elevated working temperature (> 950 ◦ C), owing to their volatility. Zn
and Pb concentrated in the collected dust can be further extracted by
selective leaching. The leaching solution would be deep processed using
the respective means for recycling Zn and Pb (Li et al., 2019b; Guo et al.,
2018a; Liu et al., 2019c).
In the past decades, numerous studies were conducted to further
improve the metallurgical recycling efficiency, especially for the
extraction of iron from copper slag, which refers to the corresponding
reduction parameters, including reduction temperature and duration,
reducing agent, and additive (including flux), as well as the grinding-
magnetic separation parameters, such as fineness, magnetic field in­
tensity, and liquid to solid ratio. The main results are listed in Table 5.
The optimisation of an additive gradually becomes a research emphasis
and hotspot for a more efficient method to recycle the copper slag.
As described above, iron and copper in the slag are commonly
difficult to recycle via reduction roasting process because of they are
mainly present in the form of fayalite and copper sulphide, respectively.
However, the recovery efficiency can be improved by adding some ad­
ditives, such as CaO, calcium salts (CaCO3, CaMg(CO3)2), sodium salt
(Na2CO3), and iron oxides (Fe2O3, Fe3O4) during the direct reduction
process (Zhang et al., 2019b; Liu et al., 2019c; Zhou et al., 2015; Li et al.,
2019b). Among these additives, the combination of CaO and Na2CO3 is
testified as the most effective one. The mechanism of Na2CO3 and CaO
added for promoting the reduction of copper slag is illustrated in
Fig. 10, which demonstrates that significant amounts of iron and copper
sulphides (matte (Cu2S-FeS)), and fayalite (Fe2SiO4), being the main
copper-bearing and iron-bearing minerals, were still present in the
reduced products without CaO and Na2CO3. However, with the addition
of 8% Na2CO3 and CaO at basicity of 0.5, the matte and fayalite almost
disappeared, which implies that almost all of the sulphides and fayalite
has transformed to the phases of metallic state (Li et al., 2019b).
Furthermore, the main elemental distribution behaviours of the reduced
products shows that not only iron and copper distributed together
resulted in the formation of an Fe-Cu alloy, with the mean particle size of
the metallic phase evidently increased, but also there was an obvious
dividing line between the gangue phase and the metallic phases, which
was beneficial to an suitable liberation of the metallic phase from the
gangue phases at the subsequent fine grinding stage. Furthermore, it was
also conducive to a preferable separation of Fe and Cu and significantly
improving the recycling of iron and copper from the slag.
4.4. Smelting reduction
High temperature reduction followed by smelting separation (known
as smelting reduction) is an effective method for the metallurgical
recycling of copper slag. Commonly, the high temperature reduction of
metallic oxides (or sulphides) in the copper slag, and smelting separa­
tion from each other are conducted in a single electric arc furnace. Thus,
the reduction behaviour of metal-bearing phases and the differences in
the density and fusibility between the molten metals and the secondary
slag are both key points for the metallurgical recycling of copper slag.
Many studies have testified the process as being efficient for the
treatment of copper slag with high contents of silicon and iron, as well as
copper slag containing copper, zinc, and lead. A flowchart of smelting
reduction in an electric arc furnace is illustrated in Fig. 11. Raw mate­
rials composed of ground copper slag, reductant (e.g. coke and coal),
and flux (e.g. CaO, CaF) are charged into the furnace. The binary basicity
(CaO/SiO2) of the mixture is generally below 0.6, and the operation
temperature range of the electric arc furnace is 1350–1550 ◦ C (Sarfo
et al., 2017b; Heo et al., 2013). During the smelting reduction process,
the metallic oxides and sulphides (e.g. Fe2SiO4, Fe3O4, Fe2O3, Cu2S,
CuO, ZnS, ZnFe2O4, PbS, and PbFe2O4) in the copper slag can be usually
reduced to their respective metallic states by the addition of a reductant
and flux at the high molten state, while gangue minerals form a
H. Tian et al. Resources, Conservation & Recycling 168 (2021) 105366

Table 5.
Metallurgical recycling efficiency of reduction roasting followed by magnetic separation process.
Composition of copper slag (wt.%) Reduction and magnetic separation conditions Grinding Magnetic Grade/Recovery (wt.%/%) Ref.
Fe Cu Zn Pb SiO2 T Time Reductants Additives fineness field concentrates Dust
(◦ C) (min) intensity Fe Cu Zn Pb

40.78 0.25 1.35 0.51 33.20 1280 35 25wt.% 10% 72% 143.31kA/ 90.35 NR NR NR Cao
anthracite Limestone passing m /89.70 et al.,
3% Na2CO3 74 μm 2016)
40.33, 0.65 NR 0.079 32.33 1250 80 soft coal (C/ 10% 83% 1800 Gs 90.31/ 1.55/ NR NR Cuo
Fe=1.8) Na2CO3 passing 95.08 85.33 et al.,
74 μm 2017
39.74 0.70 NR 0.21 34.5 1250 90 25 wt.% coke None 75-104 0.03T 66.1/ 1.0/ NR NR Kim
μm 87.03 75.9 et al.,
2013
40.33 0.65 1.11 0.79 32.33 1250 80 bituminous 8% Na2CO3, 85% 1000 GS 94.3/ 86.5/ 50.65/ 8.56/ Li
coal(C/ Burnt lime passing 90. 1.2 92.4 91.9 et al.,
M=10)* (R= 0.5) 74 μm, 2019b
39.85 0.33 2.81 0.22 30.81 1200 70 200 wt.% Limestone 95% 0.08 T 90.68/ 0.66/ NR NR Zhou
soft coal (R=0.3) passing 90.49 79.53 et al.,
3.28% 74 μm 2015
Fe2O3
8.29%
Fe3O4
39.85 0.27 2.38 0.48 33.05 1300 35 25% semi- 10% 60% 95.54 kA/ 92.79/ NR 79.59/ NR Liu
coke Dolomite, passing m 88.12 63.87 et al.,
45 μm 2019c
31.59 0.23 1.5 0.42 25.33 1250 35 100% coal 2% Ca(OH)2 80% NR 65.83/ 0.44/ NR/ NR/ Guo
passing 89.6 82.26 90.54 96.8 et al.,
74 μm 2017a
*
C/M: coal/metal (mole ratio); NR: Not reported

Fig. 10. Mechanism of Na2CO3 and CaO added for promoting the reduction of copper slag (Reduction with Carbon/ Metals (molar ratio) of 10 at 1250 ◦ C for 80 min)
(Li et al., 2019b).

secondary slag combined with the flux. Most of the reduced zinc and
lead, which have a higher saturated vapour pressure, usually evaporate
into the dust fraction with the upward gas flow, as they have no sig­
nificant concentrations in either the pig iron or the secondary slag
(Maweja et al., 2009; Guo et al., 2018b). Most of the reduced iron and
copper dissolve mutually into a molten state and form different layers
for the separation from slag, depending on the differences in the
densities. In general, the copper grade has to be controlled below 0.5%
in the molten steel, while the copper-bearing pig iron (Cu 1%–3%) may
be reasonable in the production of wear resisting alloys (Guo et al.,
2018a). The pig iron generated from the copper slag may need some
refining before its utilisation, it should be noted that the copper-bearing
pig iron can be also diluted by blending with other pig iron samples at a
small percentage when desired.

14
H. Tian et al.
Fig. 11. Flowchart of smelting reduction for recycling copper slag in an electric arc furnace (Guo et al., 2017b; Sarfo et al., 2017b).
The smelting reduction efficiency is commonly affected by techno­
logical conditions mainly including reduction time, reduction temper­
ature, flux types, and carbon content of the initial furnace burden, which
have been described in detail through a statistically designed experi­
ment by Sarfo et al. (2017b). The smelting reduction process was con­
ducted with optimised condition of 12.5% carbon, 10% flux at 1420 ◦ C
for 75 min, and the total recovery of metal could reach nearly 90%. In
addition, many studies (Maweja et al., 2009; Starodub et al., 2016; Heo
et al., 2013) have also confirmed the superiority of the smelting
reduction process for recycling the copper slag, characterised by a
compact process flow route, high recycling efficiency, and low pollution,
while the drawback of high energy consumption and small production
scale limit further industrial application.
4.5. Molten modification followed by physical separation
Molten modification followed by beneficiation is an efficient way to
recycle iron and copper through the transformation of iron (copper)-
bearing phase in the copper slag to satisfy the demand of subsequent
beneficiation stages, which mainly include two categories, namely
molten oxidation followed by gravity and magnetic separation process,
and molten sulphidation followed by flotation and magnetic separation
process. Many experimental studies have been conducted mainly for the
molten modification stage to improve the physical separation efficiency,
and recycling of iron and copper from the modified slag.
4.5.1. Molten oxidation followed by gravity and magnetic separation
Fig. 12 illustrates the flowchart of the process of molten oxidation
followed by gravity and magnetic separation for the treatment of copper
slag and summarises the main chemical reactions of the oxides and
sulphides of iron (copper) during the molten oxidation stage. The
metallurgical recycling of iron and copper from copper slag mainly de­
pends on a transformation from nonmagnetic iron components (fayalite)
into magnetite and sedimentation of metallic copper to the bottom of
slag at an appropriate oxidising atmosphere. Then metallic copper and
magnetite can be obtained by fine grinding, combined with subsequent
gravity separation, and magnetic separation from the slag, respectively
(Cao et al., 2012). During the molten oxidation process, Fe2SiO4 and FeS
can be oxidised stepwise in the order Fe2SiO4 → Fe3O4 → Fe2O3 and FeS
→ FeO → Fe3O4 → Fe2O3, respectively, if provided with enough oxygen
partial pressure. In detail, the oxidising reaction of Fe2+ generated from
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Resources, Conservation & Recycling 168 (2021) 105366
Fe2SiO4 and FeS occurs along with the oxygen diffusion, resulting in a
higher content of Fe3+. Silica will be saturated in the molten slag and be
precipitated out of the silicate. With the generation of Fe3+, magnetite
will be generated by Fe3+, Fe2+, and O2− (Fan et al., 2015; Yao et al.,
2019). The magnetite in the molten slag would be further transformed
into hematite (Fe2O3), if an extra O2− exists. In addition, the oxidation of
FeS and Cu2S generated from the copper matte (Cu2S-FeS) will also
decrease the sulphur partial pressure to form metallic copper. To
selectively obtain as much magnetite and copper as possible, the oxygen
and sulphur partial pressure have to be suitable at the working tem­
perature, which can be illustrated in the predominant areas of the phase
diagram of the Cu-Fe-O-S system. As shown that there is a coexisting
range for magnetite and metallic copper when log (PO2/PƟ) is between
–5.6 and –2.9, and log (PS2/PƟ) is below –5.7 at 1653 K (Cao et al.,
2012). In addition, the continuous generation of magnetite will increase
the viscosity of the molten slag under the circumstance of the required
oxygen potential, which will slow down the oxygen transfer process. It is
beneficial to maintain the oxygen potential of the coexisting range
during molten oxidation process (Fan et al., 2014; Li et al., 2019a).
In addition to the conversion degree of phases, the growth of metallic
copper and magnetite fine particles during molten oxidation stage is also
essential to enhance subsequent physical separation, and improve the
recovery of copper and iron from the copper slag. Many studies have
been conducted to improve the molten oxidation efficiency through
optimisation of the experimental factors, such as oxygen partial pres­
sure, oxidation temperature, oxidation time, additives, and cooling rate.
(Liu et al., 2019b; Lai et al., 2017; Cao et al., 2012; Guo et al., 2017b;
Jiang et al., 2016). In contrast to the pure oxygen gas, air or even a low
proportion, typically 1–3 vol%., of oxygen with the remainder being
nitrogen (or argon) is more beneficial because of the controllable oxygen
concentration. Simultaneously, at the required oxygen partial pressure,
the more effective stirring action of the blown gas can relieve the
adverse effect of increased viscosity, caused by the generation of
magnetite from fayalite. The low viscosity of the slag can increase the
collision probability of the metallic copper and magnetite fine particles,
respectively, and then further improve the growth of the grain size.
Furthermore, with the addition of additives, such as CaO, CaF, and
Na2CO3, the holding time increases and slow-cooling yields a similar
effect. Simultaneously, adding additives is also beneficial to decreasing
the activation energy of Fe2SiO4, oxidised to Fe3O4, and improving the
molten oxidation efficiency. Under the influence of various beneficial
H. Tian et al.
Fig. 12. Flowchart of the molten oxidation followed by gravity and magnetic separation process for the treatment of copper slag and the main chemical reactions of
the oxides and sulphides of iron (copper) during the molten oxidation stage (Cao et al., 2012; Fan et al., 2015).
conditions at 3% CaO, combined with 1% CaF added, the modification
temperature at 1380 ◦ C for 60 min, air velocity of 7 L/min for 5 min, and
a cooling speed of 1.0 ◦ C/min to 1200 ◦ C, the grain size of magnetite and
copper particles can effectively grow larger than 60 μm in the modified
slag. As a consequence, the grade of iron in the magnetite concentrate
and copper in crude copper can achieve 60.19 wt.% and 92.27 wt.%
from the modified slag, followed by subsequent grinding and separation
stages, with corresponding recovery rates of 90.0% and 62.32%,
respectively (Cao et al., 2012).
4.5.2. Molten sulphidation followed by flotation and magnetic separation
A flowchart of the molten sulphidation process for the treatment of
copper slag and the resultant sulphidation behaviour of the modified
slag compared to that of the unmodified one, is illustrated in Fig. 13. As
shown that the molten sulphidation, followed by flotation and magnetic
separation primarily includes five stages, namely (1) crushing and
screening the initial slag, (2) adequately mixing between the slag and
additives, (3) charging the feed to molten sulphidation reaction at a
16
Resources, Conservation & Recycling 168 (2021) 105366
suitable temperature followed by slowly cooling, (4) recycling the
copper concentrate by flotation, and (5) separating the magnetite by
magnetic separation. During molten sulphidation of the copper slag,
some suitable flux and additive are usually added to not only achieve a
phase transformation from Fe2SiO4 to Fe3O4, and from CuO to CuS, but
also increase the liquidity of the molten slag to accelerate the migration,
aggregation, and growth of the target fine mineral grains. The added flux
(e.g. CaO) can react preferentially with SiO2 to generate CaO•SiO2 and
simultaneously take the place of FeO in the Fe2SiO4, leading to an
improvement in the activity of free FeO released into the slag (Zhang
et al., 2008; Lai and Huang, 2017). As a consequence, the FeO released
reacts with Fe2O3 to form more Fe3O4. In addition, according to the
chemical composition of the copper slag, especially for the proportion of
the copper oxides, a compound additive containing Fe2O3, sulphides (i.
e. FeS, FeS2), and an assistant viscosity reducer (i.e. MnO) is added in
powder form for sulphidation treatment. This helps recover copper
sulphide from the slag, which then enters the matte phase (Guo et al.,
2018c). In addition, moderate sulphides can react with Fe3O4 to control
H. Tian et al.
Fig. 13. Flow chart of the molten sulphidation process for the treatment of copper slag and sulphidation behaviour of the modified slag compared to that of the
unmodified slag (Guo et al., 2016; Guo et al., 2018c).
the proportion at a reasonable level, combined with the assistant vis­
cosity reducer for an appropriate viscosity of the molten slag. The ex­
istence forms of iron and copper in their corresponding minerals by the
molten sulphidation treatment are summarised in Fig. 13. As shown that
the proportion of Fe in the form of magnetite, and Cu in the form of
copper sulphide increased from 32.9% to 65.1%, and 80.0% to 90.3%,
respectively. Furthermore, copper matte grains in the unmodified slag
with a fine size less than 10 μm, combined with filamentous magnetite,
were finely dispersed throughout the slag, and surrounded by fayalite.
These were difficult to liberate during the subsequent fine grinding
stage, leading to a poor flotation and magnetic separation efficiency. In
contrast, the particles of magnetite and matte grew significantly with
sizes exceeding 50 μm after the molten sulphidation treatment. To
obtain the above beneficial effect, a suitable cooling speed and terminal
cooling temperature of the molten slag were equally important. The
molten phases were beneficial to the rapid grain coarsening of magnetite
and matte, in which the smaller particles would enter into the solution
and deposite on the larger ones, thus improving the mass transfer and
fluidity as a solid would have a slower diffusion velocity than a liquid
(German et al., 2009; Shi et al., 2019). Hence, to ensure sufficient
diffusion, aggregation, and coarsening of magnetite and matte grains
from the molten state to the solid state, the terminal temperature of the
retarded cooling of the molten slag need not be above the lowest tem­
perature of phase transformation for the target minerals, e.g. Cu2S-FeS
(950 – 1100 ◦ C). Simultaneously, a retarded cooling speed of 1 – 2
◦
C/min proved to be an appropriate temperature interval. At the opti­
mised conditions, specifically a 12% compound additive (containing
FeS, Fe2O3, and MnO) of 12%, binary basicity of 0.45, modifying at
1350 ◦ C for 120 min, and cooling speed at 1.5 ◦ C/min down to 900 ◦ C,
the grain size of magnetite and copper matte was predominantly above
50 μm in the modified slag. The results of studies showed that for the
modified slag, the copper grade of concentrate was raised from 6% to
11% with maintaining similar recovery of nearly 72%, and the Fe re­
covery of concentrate was raised from 32% to 63% with maintaining
17
Resources, Conservation & Recycling 168 (2021) 105366
similar Fe grade (Guo et al., 2016; Guo et al., 2018c).
From the above, it is learnt that molten modification followed by a
physical separation process, as a new enrichment technique for the
recycling of Cu and Fe from the copper slag has been developed in recent
years; however, the process also has many disadvantages, such as long
process flow, multiple restrictive links, strict atmosphere requirement;
and high proportion of additives. It needs to be further studied to
address the above shortcomings and to facilitate its application to large-
scale industrial production.
5. Discussion
As a typical and considerable by-product obtained from the copper
smelting industry, copper slag contains not merely valuable metals (e.g.
Fe, Cu, Zn, Pb, Ni, and Co), but some undesired harmful elements (e.g.
As, Hg, Bi, and Sb). Unfortunately, more than 80% of the copper slag,
worldwide, is discarded directly without a suitable treatment, which not
only wastes the limited sources of valuable metals, but dispossesses
precious land, and simultaneously causes damage to the ecology.
Although partial copper slag has been applied as an additive to produce
value-added products in civil engineering applications, owing to its
versatile properties, the presence of a large proportion of metals in the
copper slag will limit its civil applications. It is certainly a wastage of the
secondary metal resources. Based on the above background, compatible
treatment processes, namely flotation, leaching, reduction roasting fol­
lowed by magnetic separation, smelting reduction, and molten modifi­
cation followed by physical separation have been certified appropriately
for metallurgical recycling from different types of copper slags.
Despite notable progress made in this field, there are still some
technical and environmental challenges/problems warranting (1) a
further improvement of the metallurgical recycling efficiency, (2)
removal and immobilisation of harmful elements, and (3) effective uti­
lisation of the cleaned secondary slag. These are deemed indispensable
for green and sustainable development of the treatment processes of
H. Tian et al.
copper slag. To some extent, the solution methods can also represent the
key point of industry development and technological innovation in
metallurgical recycling and refined cleaning of copper slag.
To cope with the first problem for preferable extraction of valuable
metals from the copper slag, more efforts should be directed to one or
more objectives among high efficiency, energy conservation, and
emission reduction for treatment processes. As mentioned earlier, the
flotation process can obtain desirable recycling for copper as a form of
sulphide and metallic state from the copper slag via slow-cooled treat­
ment. However, with the improvement of flash smelting process for the
extraction of copper, needing high oxygen-containing gas blowing, the
content of CuO in the copper slag has been increasing (Zhai et al., 2019).
On the other hand, CuO has poor floatability and cannot be recovered
effectively by the flotation process. Thus, a vulcanising agent such as
Na2S is added into the ore pulp for the sulphurisation of CuO to generate
CuS and improve the floatability. It should be emphasised that an excess
of Na2S will suppress the floatability of CuS; hence it needs to be added
in moderation and in batches (Sarfo et al., 2017b). An ore pulp pH of
8.5–9.5, which can be adjusted by CaO is the key for a beneficial effect of
Na2S. The addition of Na2S combined with ammonium sulphate in 1:1
ratio can further improve the recovery of copper because the concen­
tration of HS− benefits the sulphidation reaction and the floatability of
CuO (Sun et al., 2019). Guo et al. (2018c) have provided an innovative
technique for the phase transformation from copper oxide into copper
sulphide, and the increase in size of copper sulphide fine particles from
several microns to nearly tens of microns, by the addition of a composite
additive (containing 40.5% S, 42.3% Fe, and 15.6% fixed carbon), as the
molten slag was added into a pouring basket for slag modification and
retarded cooling. Compared to the initial slag, the recovery of Cu was
improved evidently from 69.2% to 73.4%, with Cu grade of the
concentrate was increased marginally from 20.2% to 21.7% via the
subsequent flotation stage for the slag under modified treatment. For
chemical leaching, an improved high-pressure oxidative acid leaching
process was tested by Perederiy et al. (2011) to evaluate the perfor­
mance of the pyrrhotite tailings, fed as one of the alternatives to sul­
phuric acid, depending on the reaction among the pyrrhotite tailings,
O2, and H2O to generate H2SO4 under a condition of high-pressure at­
mosphere. The leaching experiment of pyrrhotite tailings with copper
slag at 250 ◦ C, 90 psi O2, and 68 g/L tantamount stoichiometric H2SO4
(generated by addition of the pyrrhotite tailings weight at 25% of the
mixture) was proved to have similar kinetic characteristics compared to
the addition of sulphuric acid. The final extraction of Cu, Ni, and Co
were all more than 90% leached for 20 min and reached 97% within 45
min. It is worth emphasising that the acidity was gradually elevated in
the co-leaching system at the first 10 min, depending on the system
pressure level for the efficiency of acid re-generation. Furthermore, an
oxygen overpressure of more than 90 psi could obviously accelerate the
efficiency of acid generation resulted in the earlier stages of co-leaching
for the dissolution of valuable metals. Moreover, the pre-treatment of
copper slag before chemical leaching process is emerging as a research
hotspot and as an effective means to increase leaching performance, and
simultaneously decrease the addition of leaching reagents and time.
Anand et al. (1981) studied the leaching experiment used ferric chloride
as a leaching agent with and without pre-treatment, and proved that the
leaching agent was efficient for leaching valuable metals from the cop­
per slag, especially as pre-treatment (e.g. reduction roasting) for the slag
was employed before the leaching stage. Ferric sulphate selected as the
leaching agent was also one of the alternatives to obtain preferable
leaching performance with a prior treatment of high temperatures
(Carranza et al., 2009b), or ferric sulphate/sulphuric acid and ultra­
sound (Beşe, 2007). Miganei et al. (2017) tried pre-roasting a copper
slag at 800 ◦ C for 30 min to substitute the addition of 50 kg of H2O2 per
ton slag resulting in the same copper leaching efficiency of 80%–90%.
Turan et al. (2019) studied the leaching efficiency of copper slag by
addition of acetic acid hydrogen peroxide as lixiviant combined with the
ultrasound treatment, and the results showed that the ultrasound
18
Resources, Conservation & Recycling 168 (2021) 105366
leaching was twice as fast as the agitation leaching at the optimal
experiment parameters of 4 mol/L CH3COOH, 2 mol/L H2O2, 10% of
ultrasonic power, and 1:25 of solid-liquid ratio at 65 ◦ C for 60 min,
resulting in a selective leaching with recoveries of 93%, 27%, and 3% of
Cu, Zn, and Fe, respectively. For the bioleaching process, modification of
survival conditions for microorganisms through addition of suitable
elemental sulphur and inorganic acid or supply of high acidity culture
medium required for the generation of energy (e.g. sodium chloride,
glucose, ammonium sulphate, etc.) can further improve the bioleaching
efficiency (Panda et al., 2015). For instance, the addition of (NH4)2SO4
benefits the recycling of Co and Ni, while NaCl addition can lead to a
preferable leaching results of copper. When nutrient solutions were
applied to the culture medium, a higher proportion of Fe2+/Fe3+ was
obtained because of the better adaptability of bacteria. The addition of
sulphur allowed obtaining a greater leaching efficiency, depending on
the bacterial oxidation of sulphur. This led to the formation of sulphuric
acid that accelerated the recycling of metals from the copper slag. At
present, the bioleaching process develops rapidly and gradually be­
comes one of the most promising technologies with clean and
eco-friendly characteristics for the separation, extraction, and enrich­
ment of valuable metals from the copper slag. Therefore, the research on
screening suitable microbial strain and searching the appropriate con­
dition to cultivate the microorganisms is the hotspot in bioleaching for
the treatment of copper slag. In addition, as described earlier, reduced
metallic copper from copper slag is inevitable to dissolve into the
iron-rich alloy during the reduction process, which works against the
separation of iron and copper. Some researchers tried to realise the
separation efficiency and recover copper before or after making the pig
iron by the flotation process for prefetching the copper-bearing phases
(Chen et al., 2019), or treatment with aluminium sulphide-ferrous sul­
phide flux, in order to obtain a matte phase. It is favourable to remove
the copper in the pig iron by adopting suitable processes before its uti­
lisation in the steelmaking to some extent (Shimpo et al., 1997). While
taking into consideration from another point of view, in comparison
with the utilisation of cathode copper for the production of
weather-resistant steel, using iron-copper alloy, obtained by reduction
process, as the ingredient or partial substitution of electrolytic copper,
was regarded more significant, which can effectively go against the
squander energy of separation between Fe and Cu, before the combi­
nation with each other at high temperature. Furthermore, for the pro­
duction of weathering steel, in addition to the electrolytic copper, the
requisite number of nickel cathode are also used to satisfy the chemical
composition of the weathering steel, leading to a high production cost.
Guo et al. (2017b) studied the reduction behavior of copper slag com­
bined with nickel laterite to produce ternary (Fe-Cu-Ni) alloy for
weathering steel, which provides a cost-effective and
environmental-friendly method for the treatment of copper slag. The
liquidus temperature of the high-melting nickel laterite can be obviously
decreased by co-reduction with copper slag because of its high FeO
content, which contributes to the migration efficiency of the metallic
ions, and growth of fine metallic particles to meet the requirement of
subsequent magnetic separation process. A crude Fe-Cu-Ni alloy with
1.1% Cu, 2.5% Ni, and 87.9% Fe can be produced with corresponding
recovery rates of 78.7%, 87.2%, and 69.0%, respectively. There will
gradually be a tendency for the utilisation of the crude multi-component
alloy to partly replace the electrolytic metals in the alloy steel industry,
which contributes to the development of the reduction process for the
treatment of copper slag. Furthermore, for the reduction treatment of
copper slag, in addition to the additives as a promoter, a large number of
carbonaceous materials are employed in the carbothermic reduction
roasting or smelting process. In order to reduce the dosage of conven­
tional reducing agents and alleviate environmental stress, biomass, such
as pine sawdust, corncob, straw, and walnut shell (Zuo et al., 2016;
Zhou et al., 2019), as one of the renewable energy sources characterised
as widely distributed, abundant and environment-friendly, is an alter­
native to coal for realising the reduction of valuable metals in the copper
H. Tian et al.
slag, as well as reducing the dependence on traditional coals and sulphur
(carbon) dioxides emissions, owing to its higher fixed carbon and low
sulphur content. In recent years, many studies were conducted to
disclose the pyrolysis behaviour and reducing capacity of biomass, as
well as the application effect on metallurgical recycling, especially for Fe
recovery efficiency from copper slag. The reduction of copper slag with
addition of biomass generally consists of three phases, namely,
drying-pyrolysis of biomass (~ 686 ◦ C), prereduction (686 ~ 827 ◦ C)
and deep reduction (827 ◦ C ~) (Zuo et al., 2016; Zuo et al., 2018b).
Anecdotal evidence on the reduction of biomass suggests that the
biomass reducer can be simplified as a complex-state matter, including
fixed carbon and fuel gases (CO, H2 and CH4), which are the
high-temperature pyrolysis products of the biomass. The secondary
reducing agents can realise the phase transformation from metal sul­
phide (oxide) to metallic state. Furthermore, a suitable addition of CaO
can increase the recovery of valuable metals, depending on the
improved reduction efficiency and growth of the fine metallic particles,
while excessive addition will have a negative effect owing to the gen­
eration of dicalcium silicate can increase the viscosity and limit the mass
transfer effect (Zuo et al., 2018a).
The removal and immobilisation of the harmful elements are sig­
nificant and important stages during the metallurgical recycling and
cleaner treatment for the copper slag to obtain cleaned secondary slag
with low residual toxic elements. Commonly, the hydrometallurgical
processes have considerable extraction efficiency for not only valuable
metals but also harmful elements. The elements (Cu, Fe, Zn, Co, Ni, Pb,
Ce, As, etc.) dissolve in acid or alkali solution, and can be separated and
removed (or recycled), followed by subsequent filtration, washing, and
extraction by adding corresponding extraction agents. As a result, the
concentrates of leached elements decrease markedly in the secondary
slag (leaching residue). However, it is a remarkable fact that a large
portion of the liquid waste as a state of acidity (or alkalinity) should be
taken into consideration during the hydrometallurgical processes, to
avoid secondary pollution of the environment. Taking the acid liquid
waste for example, the aim of the liquid waste disposal is to force the
acid liquid waste divide into a cleaned liquid stream, and a solid stream
containing the impurity elements of liquid waste; both of them need to
be discharged to the environment in a reasonable manner or be further
applied into the suitable process. The liquid waste treatment process can
be normally divided into three stages, sedimentation of impurities by pH
adjusting agents, removal of solids from liquids, and depuration of liq­
uids for reusing. The selection of the sedimentation methods is related to
the dissolvability of the salts in the liquid phase. For example, the
neutralisation and sedimentation were simultaneously conducted
through the addition of Ca(OH)2, and then gypsum was generated. The
liquid phase can be separated easily from the solid after the sedimen­
tation of the impurities. Both of them can be recycled for further
application (Miganei et al., 2017; Roy et al., 2016).
Compared to the hydrometallurgical processes, pyrometallurgical
processes commonly have different removal behaviours of environ­
mentally hazardous trace elements. In the reduction processes, Zn, Pb,
As, and S in the copper slag can be removed beyond 90% by the addition
of Ca-based fluxes, such as CaC2, CaF2, and CaO (Sarfo et al., 2017b).
The waste ferric-oxide desulphuriser (WFD) comprising 32.33% S,
17.91% CaO, 7.89% Fe, and 5.82% C was also employed in the smelting
reduction-sulphurising process for the refined cleaning of waste copper
slag (Guo et al., 2018b). With the increase of WFD from 0 to 15%, the
removal rate of Sb, Ni, and As and improved significantly from 52.23%
to 95.51%, 43.21% to 98.94%, and 45.56% to 96.81%, respectively,
depending on the reduction and sulphidation of Sb, Ni, and As minerals
in the copper slag to sulphide or metal state, and subsequent transfer and
settling down to the matte phase. Meanwhile, the WFD also had a slight
effect on the removal of Pb, Zn, Hg, and Bi, resulting in an improved
elimination rate of greater than 90%, because of Pb, Zn, Pb, and Bi
minerals being reduced into their respective vapours, owing to their
high saturated vapour pressures during the smelting reduction process.
19
Resources, Conservation & Recycling 168 (2021) 105366
Hence, they can be easily recycled from the cooled flue gas. Further­
more, the toxicity characteristic-leaching procedure test was employed
to measure the environmental implication of the cleaned secondary slag,
which revealed that the harmful scale of the leachate was within limits
of the thresholds prescribed in USEPA-2017. This verified that the
cleaned secondary slag with the residual harmful elements was secure
enough for human and environment.
To effectively reuse the cleaned secondary copper slags in suitable
fields, the chemical compositions and physical properties are the
important standards for evaluation. The utilisation of calcium silicate, i.
e. the leaching residue of copper slag after neutralisation and precipi­
tation treatment by the addition of slaked lime, was investigated and
proved to be a good alternative for the cement additive. A study con­
ducted by Miganei et al. (2017) found that the leaching residue had a
similar composition as Portland cement. The mainly influential factors
to the cement was the silica modulus, manifested by the proportion of
SiO2 to the total Fe2O3 and Al2O3, which affects the solidifying velocity
of the cement. Commonly, a silica modulus of 2–3 can meet the product
requirements. Furthermore, the hydraulic modulus is another important
indicative value, derived from the proportion of CaO to the total
amounts of SiO2, Al2O3 and Fe2O3, and typically equals 1.7–2.3. The
calculated silica modulus and hydraulic modulus of the leaching residue
from the copper slag are both held within reasonable ranges by the fine
adjustment of calcium content. For the secondary copper slag obtained
from the reduction processes, the metal elements, especially the iron
content decreased markedly in comparison to the initial slag. On the
contrary, the content of silica, calcium, and aluminium increased. Based
on the above estimations, the secondary slag is inclined to the applica­
tion into the glass, propping agent, and ceramic industry as the corre­
sponding feed; however, as at least two of the major properties are
satisfied, i.e. adequate hardness (> 657.4 VHN) and low density (< 2.73
g/cm3) (Sarfo et al., 2017b). While the requirements can be completely
reached through the addition of flux for adjusting the slag type during
the reduction process. In that sense, the secondary slag after extraction
of valuable metals and removal of harmful elements can be reused as a
environmentally-friendly functional material, in comparison to the
conventional treatment for waste copper slag.
6. Conclusion
Copper slag, a hazardous waste generated primarily during copper
smelting is an important secondary resource containing a large number
of valuable elements. A sustainable waste utilisation, including metal­
lurgical recycling and refined cleaning of the copper slag is considered a
more preferred option than dumping or disposing it untreated in view of
its potential economic and environmental benefits. The authors, in this
study, have reviewed the generation mechanism, chemical/physical
characteristics of the copper slag, and the main metallurgical processes
for recycling and cleaning the slag. It was revealed that although copper
losses could be controlled typically at the level of 0.55–1.3 wt.%,
depending on the optimisation of the copper smelting condition, fol­
lowed by a subsequent electric cleaning furnace, the final slag, as well as
other historically abandoned copper slag still contained large amounts
of valuable metals, such as Fe, Cu, Zn, Ni, and Co, and toxic elements,
such as Pb, and As. Thus, the slag urgently needs to be subjected to
further metallurgical recycling and refining. In addition, based on the
characteristics of the copper slag, such as a relatively complex phase
composition, super micro-grained dissemination, and maldistribution of
valuable and harmful elements, it was determined that it commonly
needed to be treated by a combination of one or more methods, such as
beneficiation, chemical treatment, and high-temperature processing for
the efficient separation of target products from impure elements or
gangue minerals.
Suggested methods for metallurgical recycling from the copper slag
mainly include pyrometallurgical processes (e.g. reduction roasting,
followed by magnetic separation, smelting reduction, and molten
H. Tian et al.
oxidation), hydrometallurgical processes (e.g. chemical leaching and
bioleaching) and beneficiation processes (e.g. flotation and magnetic
separation). The flotation process is relatively efficient only for the re­
covery of copper sulphide and mechanically entrained metallic copper
from a slow cooling copper slag; however, it can also be applied to other
processes as a pre-treatment for the prior recovery of copper. Even
though chemical leaching can realise selective extraction of valuable
metals and simultaneous removal of harmful elements, it still has defects
owing to the high consumption of leaching and oxidising agents, as well
as heavy environmental pollution. On the other hand, bioleaching has
developed into a viable alternative to the traditional chemical leaching,
to realise metallurgical recycling of copper slag and simultaneously
resolve the aforementioned deficiency. Reduction processes also present
good metallurgical recycling efficiency for the copper slag, and most of
the reduced iron and copper dissolve mutually, and are transferred to
alloy phase, while most of the reduced zinc and lead, which have higher
saturated vapour pressures usually evaporate into the dust fraction with
the upward gas flow. Compared with smelting reduction, reduction
roasting, followed by magnetic separation can significantly decrease the
energy consumption and operational cost. During the reduction roasting
stage, the reduction of fayalite and copper sulphide in the copper slag,
and the growth of Fe-Cu alloy particles are the key for the subsequent
magnetic separation, and hence affect the recycling efficiency. The ef­
ficiency can be improved by the addition of suitable additives. For
molten modification followed by physical separation, iron and copper in
the copper slag can be obtained in the form of magnetite and metallic
copper (or matte), respectively. During the molten modification stage,
the growth of magnetite and metallic copper (or matte) particles is
essential to enhance the subsequent physical separation and improve­
ment of the recovery of copper and iron from the copper slag. However,
a continuous generation of magnetite would increase the viscosity of the
smelting slag, thus adversely affecting the mass transfer and aggregation
of fine particles. This further limits the recycling efficiency of the copper
slag; therefore, the content of magnetite in the molten slag, controlled at
an appropriate level should be taken into consideration.
Despite an obvious progress in this field, some technical and envi­
ronmental challenges/problems still exist in this area that require
further improvement of metallurgical recycling efficiency, removal and
immobilisation of the harmful elements, and effective utilisation of
cleaned secondary slag, deemed as indispensable factors for the green
and sustainable development of the treatment processes of copper slag.
Thus, improved processes for the metallurgical recycling and cleaning of
copper slag, characterised by a high recycling efficiency, low energy
consumption, and low secondary environmental pollution are still the
research focus and development trend in this area.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was financially supported by the Youth Natural Science
Foundation of China (No. 51904347), the National Natural Science
Foundation of China (No. 51574281), the Youth Natural Science
Foundation of Hunan Province (No. 2020JJ5726) and Innovation-
Driven Project of Guangxi Zhuang Autonomous Region (No.
AA18242003).
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