Pan 2019

Resources, Conservation & Recycling 146 (2019) 140–155
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Resources, Conservation & Recycling

journal homepage: www.elsevier.com/locate/resconrec
A review on lead slag generation, characteristics, and utilization T

a a a a,⁎ b c
De’an Pan , Lili Li , Xi Tian , Yufeng Wu , Na Cheng , Hailiang Yu
a
Institute of Circular Economy, Beijing University of Technology, Beijing 100124, PR China
b
Shenyang Zhongke Ecological Environmental Assessment Co. Ltd, Shenyang, PR China
c
State Key Laboratory of High Performance Complex Manufacturing, Central South University, Changsha 410083, PR China
A R T I C LE I N FO A B S T R A C T
Keywords: Lead slag is produced by the primary and secondary lead industry. The large amount of lead slag discharge
Lead slag causes environmental problems. Reducing the toxicity and increasing utilization of lead slag are important
Recovery of metals measures to solve the negative impact of lead slag on the environment. Here, we review the lead slag physical
Utilization and chemical characteristics, as well as environmental impacts. This review focuses on the utilization of lead
Toxic elements
slag: recovery of metals and used for construction materials. Various processes for metal recovery including
pyrometallurgical, hydrometallurgical, and bioleaching methods are summarized. Coal-based direct reduction is
a typical pyrometallurgical technology for recovering metals from lead slag, which has the characteristics of high
recovery efficiency, high energy consumption and suitable for industrial production. Chloride, acetic acid, and
HNO3-based leaching systems are mainly used in hydrometallurgy of lead slag. The waste reagents and residues
produced in hydrometallurgy process inevitably increase the environmental risk. Bioleaching is an en-
vironmentally friendly technology, but it is currently limited to laboratory scale. We also discuss the utilization
of lead slag in construction materials. The use of lead slag in road construction and concrete will cause en-
vironmental risk of leaching toxic elements. The utilization rate of lead slag in cement clinker is extremely low.
Geopolymers and glass-ceramics have good stabilization effect on toxic elements. However, the extensive use of
alkaline activators limits the large-scale application of geopolymers. High energy consumption of glass-ceramics
should be considered. Finally, the limitations and prospects for future research of lead slag utilization are also
considered.
1. Introduction secondary lead recycling process, for each ton of metallic lead pro-
duced, 100–350 kg of slag are generated (Kreusch et al., 2007). Ac-
Lead is an important non-ferrous metal with broad applications in cording to the data of the World Bureau of Metal Statistics, the global
batteries, machinery manufacturing, and medicine. Both primary lead lead production is 11.1 million tons in 2016, and the lead slag pro-
ores (mainly galena-rich (PbS)) and secondary resources (mainly waste duction exceeded 5.5 million tons (Fig. 1).
lead-acid batteries) are used as raw materials for lead production (Chen At present, lead slag is mainly used in rough disposal, such as
et al., 2009). In developed countries, lead resources mainly come from landfill and stockpiling, which requires extensive land. According to
secondary lead in recovery process. More than 80% of lead production statistics, the accumulation of 10,000 t of waste residue will need to
in the United States is produced from secondary lead, and 90% of lead account for more than 670 m2 of land (Dong, 2001). Lead slag contains
production in Europe is produced from secondary lead (Zhang et al., certain highly migratory toxic elements, such as lead, zinc, and cad-
2016a, 2016b). For developing countries with China as an example, mium (Seignez et al., 2008). Under weathering and leaching conditions,
recycled lead accounts for 42% of total lead production in 2016. The the release of toxic elements is affected by mineral phases in slag (Ettler
proportion of secondary lead produced globally is 60–66%. (Zhang et al., 2009). The pH of leachate is also the main factor affecting the
et al., 2016a, 2016b). release of toxic elements from lead slag (De Andrade Lima and
Large amounts of lead slag are produced during the production of Bernardez, 2013). The toxic elements in the landfill and the accumu-
primary lead and secondary lead. Considering lead concentrate lation process will pollute the surrounding environment of the soil and
smelting as an example, a primary lead smelting system production of groundwater (Chai et al., 2015). There is a risk of enrichment for toxic
1 t of lead will discharge 7100 kg of lead slag (Hou, 2011). At the elements in plants and animals, which, ultimately, will directly or
⁎
Corresponding author.
E-mail address: [email protected] (Y. Wu).
https://doi.org/10.1016/j.resconrec.2019.03.036
Received 27 August 2018; Received in revised form 23 March 2019; Accepted 25 March 2019
0921-3449/ © 2019 Elsevier B.V. All rights reserved.
D. Pan, et al. Resources, Conservation & Recycling 146 (2019) 140–155
Fig. 1. The lead production and lead slag production from 2006 to 2016 in the world.
indirectly endanger human health. It has been confirmed that people

living near landfill slag are affected by toxic elements (Gulson
et al.,2004; Da Silva et al., 2017). If lead slag cannot be disposed in a
timely and effective manner, it becomes a severe problem for the en-
vironment.
In addition, lead slag contains great amounts of silicon, calcium, as
well as iron, copper, and other valuable metals, which can be reused as
secondary resources (Yang et al., 2014; Yu et al., 2011). Improper
disposal of lead slag can cause critical waste of resources. Therefore, the
urgent problem that needs to be solved to ensure the sustainable de-
velopment of the lead smelting industry is to achieve the reduction,
resource, and harmless utilization of lead slag.
To solve the lead slag problem, two different efforts have been
made. The first effort is to reduce the risk of toxic elements in lead slag.
Toxic elements can be extracted by means of pyrometallurgy and hy-
drometallurgy; moreover, they can be immobilized in a solidification/
stabilization product, such as a geopolymer (Guo et al., 2017; Kim et al.,
2017a, 2017b; Wang et al., 2017). The second effort to reduce the
amount of lead slag is to promote the utilization of lead slag. Certain
researchers have affirmed that lead slag can be used successfully as an
aggregate for road construction and concrete owing to its favorable Fig. 2. A typical flow sheet for primary lead production by sinter plant–blast
physical and mechanical properties (Alwaeli, 2017; Buzatu et al., furnace route (Sohn and Olivas-Martinez, 2014).
2015). The possibility of the leaching of toxic elements is the key factor
that affects the use of lead slag in production.
The purpose of this review is to provide reasonable suggestions for
the disposal of lead slag. Starting from the production of lead slag, we
will describe the physical and chemical characteristics of lead slag.
Then, we will introduce the recovery of metals from lead slag, including
pyrometallurgy, hydrometallurgy, and bioleaching technology. An in-
troduction of various utilization of lead slag will be given in details. At
last, a prospect of comprehensive utilization will be presented as well.
2. Generation and characteristics of lead slag
2.1. Generation of lead slag
Lead slag is a by-product of lead production process, mainly from

two ways: lead ore smelting and waste lead-acid battery recovery
(Ettler and Johan, 2014). Fig. 3. A typical flow sheet for primary lead production by direct smelting-
The production of primary lead is a process of extracting lead from reduction route (Sohn and Olivas-Martinez, 2014).
lead sulfide concentrate by smelting. Smelting process mainly includes
sinter plant–blast furnace route and direct smelting reduction process as furnace charged with coke. Flux (lime, silica, and ironstone) is also
shown in Figs. 2 and 3, including oxidation, reduction, and refining added to decrease the melting temperature and form a molten slag in
(Sohn and Olivas-Martinez, 2014). In sinter plant–blast furnace route, which the iron oxides are removed (Sohn and Olivas-Martinez, 2014).
PbS is oxidized in solid state to remove sulphur and PbO is produced at The direct smelting reduction process means that oxidation and
the same time. PbO is then reduced to metallic Pb, typically in a blast
141
Fig. 4. Phase diagram CaO-FeO-SiO2 system (Sinclair, 2009).
reduction steps take place in a single unit, including KIVCET, QSL, et al., 2011; Pan et al., 2019).
Kaldo, and Isasmelt/Ausmelt processes (Sinclair, 2009). Because the
PbCO3 = PbO + CO2 (3)
pouring process is incomplete, Pb and metal sulfides are left in the
molten slag (Sobanska et al., 2016). After the slag is removed from the 2PbO + C = 2Pb + CO2 (4)
furnace, it is quenched with cold water to form lead slag. The slag
produced in lead smelting is mainly CaO-FeO-SiO2 system as shown in PbO2 + C = Pb + CO2 (5)
Fig. 4 (Gregurek et al., 2015). PbSO4 + 2C = PbS + 2CO2 (6)
Waste lead-acid batteries are the main source of secondary lead,
accounting for more than 85% of the total secondary lead. (Smaniotto PbS + Fe = Pb + FeS (7)
et al., 2009). Thus, in this review, the lead slag produced during the
PbSO4 + 2Na2CO3 + 2Fe + 5C = 2Pb + 2FeNa2S + 7CO2 (8)
recovery of waste lead acid batteries will be discussed. At present,
nearly 95% of the recovery plants for spent lead acid batteries are based The addition of iron can cause the production of certain impure
on pyrometallurgical methods (Zhang et al., 2016a, 2016b). In the re- metals, such as nickel, copper, and zinc. Iron and copper exist as sul-
covery process of secondary lead, lead sulfate (PbSO4) and lead oxides phide in the slag. Sand is used to fix impurities or unnecessary sub-
(PbO and PbO2) from waste lead acid batteries are reduced to metallic stances (mainly iron ions) in the calcium silicate matrix, forming cal-
lead (Pb). The traditional pyrometallurgy process includes the two cium–iron–silicate based slag (Penpolcharoen, 2005).
types: direct smelting and indirect smelting (Sun et al., 2017). In direct
smelting, the smelting temperature of lead paste in waste lead-acid 2.2. Physical and chemical characteristics of lead slag
batteries is over 1000 °C. Reducing agent and flux such as iron, sodium
carbonate are added to the smelting process. The indirect smelting has Primary lead slag and secondary lead slag have similar physical
good environmental efficiency, which can remove most of the sulfur properties. They have a black color and a glassy appearance. The
from the paste before smelting (Li et al., 2017a, 2017b, 2017c). A ty- density of lead slag varies between 3.6 and 3.9 g/cm3 owing to the high
pical flow chart of secondary lead recovery in indirect smelting is content in iron oxide. The particle size of lead slag is between 0.1 and
shown in Fig. 5 (Ellis and Mirza, 2010). Sulfur removal is the first step 4 mm (Barna et al., 2004). The specific gravity of lead slag is
in the production of refined lead. Hydrometallurgical removal of sulfur 2.65–3.79 g/cm3, which means that lead slag is similar to ordinary
is an environment-friendly technology, which transforms lead sulfate to natural aggregates (Penpolcharoen, 2005).
carbonate and hydroxide (Morachevskii et al., 2001). The following The composition of primary lead slag changes depending on the
reactions (Eqs. (1 and 2)) are based on the fact that PbCO3 or Pb(OH)2 ores, the fluxes, and the impurities in the coke and the iron (Shoaib
have a significantly lower solubility compared with PbSO4. The in- et al., 2001). Normally, the composition of primary slag is 2.07–32.47%
soluble PbCO3 or Pb(OH)2 collected as sludge or filter cake is then Fe2O3, 9.49–28.90%FeO, 14.68–43.09% SiO2, 3.05–23.11% CaO,
transferred to the smelter. There are some differences in smelting 1.73–6.22% A12O3, 0.15–5.44% MgO, 1.12–12.28% PbO, 2.82–11.11%
technology depending on the smelter, such as Isasmelt, rotary, and ZnO, and 0.2–9.0% S. Ettler et al. studied the content of copper in
reverberatory furnace (Ellis and Mirza, 2010; Gomes et al., 2011). various types of lead slag from 4963 to 121,850 mg/kg (Ettler et al.,
2009). The composition of the secondary lead slag typically fluctuates
PbSO4(s) + 2NaOH(aq) = Pb(OH)2(s) + Na2SO4(aq) (1)
within the following ranges: 20.1–55.68% of Fe, 1.3–22.43% of Ca,
PbSO4(s) + Na2CO3(aq) = PbCO3(s) + Na2SO4(s) (2) 2.6–20.57% of Si, 0.12–1.1% of Zn, 1.15–21.97% of Pb, 0.25–1.3%Cu,
and 0.52–20.5% of S. The typical chemical components of lead slag are
In the smelting process, limestone (CaCO3) is added as flux, whereas listed in Tables 1 and 2.
coke and iron filing are used as reducing agents; lead is then recovered The mineralogical characteristics of lead slag can be determined
from the matte by reduction with iron. The following reactions (Eqs. through X-ray diffraction analysis (XRD), scanning electron microscopy
(3)–(8)) are used to describe the generation of metallic lead (Gomes (SEM), energy dispersive spectroscopy (EDS), electron probe
142
Fig. 5. A typical flow chart of secondary lead recovery in indirect smelting (Ellis and Mirza, 2010).
microanalysis, and from backscatter electron images. The mineralogical presence of oxygen in the open air enhances oxidative weathering, and
phases of lead slag are shown in the Table 3. The primary lead slag is promotes the formation of secondary oxide and carbonate phases which
mainly composed of approximately 80 wt.% CaO-FeO-SiO2 glass matrix are easier to release toxic elements. The concentration of toxic elements
and approximately 20 wt.% of other mineral phases embedded in the in lead slag increases with the prolongation of leaching time. With the
glass matrix (Sobanska et al., 2016). The mineral phases are mainly weathering and rainfall, toxic elements, such as Pd, Zn, in the slag may
identified as a complex oxide rich in iron, such as wüstite (FeO), penetrate the soil (Da Silva et al., 2017; Zheng et al., 2012), thus re-
fayalite (Fe2SiO4), and various solid solutions of spinels (franklinite sulting in toxic elements pollution if anti-seepage measures are im-
(ZnFe2O4) and magnetite (Fe3O4)) (Ettler et al., 2001, 2004). Sulfide- perfect (Deng et al., 2015). Because the toxic elements in the soil are
rich phases, such as pyrrhotite (FeS) and complex sulfides of iron, zinc not easily decomposed by microorganisms, they will migrate to the
and copper, are embedded in the glassy matrix. Zn is found in willemite plant body and impact the surrounding plants and animal growth.
(Zn2SiO4) as well. Pb exists mainly in the form of simple droplets em- Eventually, this will have a significantly harmful effect on human
bedded in the glass matrix (De Andrade Lima and Bernardez, 2011; health through the food chain (Tukker et al., 2006), such as excessive
Sobanska et al., 2016; Yin et al., 2016) . lead in the blood (Hilts, 2003).
The major compounds in the secondary slag are high concentrations On the other hand, the toxic elements in the slag may enter the
of iron complexes consisting of wüstite (FeO), pyrrhotite (FeS), and surface water and the groundwater by means of rainfall, which may
magnetite (Fe3O4),and minor amounts of fayalite (Fe2SiO4) (Kim et al., create a serious threat to local residents because of the contamination of
2017b). Lead exists as a small amount of galena (PbS), anglesite drinking water. The lead, zinc, copper and cadmium content in the
(PbSO4), litharge (PbO), and metallic lead phases. Sulfur is associated water samples from the protective pool near the landfill slag were
with iron and sodium as pyrrhotite (FeS), galena (PbS), and copper 0.150 mg/l, 0.072 mg/l, 0.042 mg/l and 0.001 mg/l respectively. (De
sulphide (Gomes et al., 2011; Lassin et al., 2007). Andrade Lima and Bernardez, 2013). In addition, lead slag can easily
become dust because of its small size in the open storage conditions. If
2.3. Environmental impacts of lead slag the toxic elements in the slag enter the atmosphere, they will cause air
pollution and even create a certain threat to human health (Da Silva
The main disposal methods of lead slag are landfill and stockpiling; et al., 2017).
these methods occupy massive land and aggravate a series of environ- Many leaching tests are conducted to assess the natural weathering
mental problems as well. The environmental stability of lead slag de- or landfill conditions of lead slag. The toxicity characteristic leaching
pends on various factors: the change of pHs, the mineral phase in the procedure (TCLP) and the EN 12457–2 leaching test proposed by the
slag, the influence of atmosphere and the interaction time between slag current American and European environmental regulations (U.S.
and water (Yin et al., 2016). Lead slag is easier to release Zn, Fe and Ca Environmental Protection Agency (USEPA, 2008; European Committee
under acidic conditions, and it easily weathered with water. The for Standardization, 2002). The purpose of the test is to classify lead
Table 1
The chemical composition of the primary lead slag (wt.%).
Fe2O3 FeO CaO SiO2 Al2O3 MgO ZnO PbO CuO S References
2.07 22.91 20.5 34.92 5.07 2.36 3.63 1.12 0.10 1.11 (Ettler et al., 2004)
10.38 23.32 22.10 24.33 2.46 2.71 11.11 3.63 – 0.39 (Seignez et al., 2007)
– 14.99 23.05 43.09 6.22 1.58 4.01 – – – (Seignez et al., 2008)
32.47 9.49 4.50 14.68 4.70 1.43 2.82 10.34 2.75 6.51 (Ettler et al., 2009)
28.81 17.56 11.53 35.50 3.85 4.65 6.02 4.03 0.79 0.24 (Ettler et al., 2009)
7.63 20.47 23.11 21.39 3.56 5.44 9.47 4.06 – 0.37 (De Andrade Lima and Bernardez, 2011)
28.10 – 23.11 21.39 3.56 5.44 9.47 4.06 – 0.37 (De Andrade Lima and Bernardez, 2013)
3.36 28.90 18.34 31.34 4.26 1.72 8.20 2.69 – 1.19 (Ettler and Johan, 2014)
8.11 23.27 22.14 24.88 2.46 2.71 10.77 3.74 – – (Yin et al., 2016)
31.57 – 3.05 21.56 1.73 0.15 6.18 12.28 1.64 8.01 (Onisei et al., 2012)
143
Table 2
The chemical composition of the secondary lead slag (wt.%).
Fe Ca Si Al Mg Zn Pb Cu S
40.8 1.3 3.0 0.75 0.26 1.0 16.7 1.2 11.2 (De Angelis et al., 2002)
55.68 11.50 17.42 2.74 1.17 – 1.94 – 4.06 (Penpolcharoen, 2005)
20.1 3.42 4.71 – – 0.12 7.43 0.25 9.54 (Knežević et al., 2010)
40.8 1.3 3.0 0.75 0.26 1.1 16.7 1.0 11.2 (De Angelis and Medici, 2012)
34.73 22.43 20.57 16.26 2.49 0.30 1.15 – 0.52 (Ettler and Johan, 2014)
50 – 3.3 – – 0.48 7.04 1.3 20 (Kim et al., 2017b)
51.4 – 2.6 – – 0.5 8.2 1.0 20.5 (Forte et al., 2017)
30.14 – 3.46 – – – 21.97 – 3.42 (Shirinbayan et al., 2014)
slag as hazardous or non-hazardous materials to determine if lead slag reduction. Wang et al. (2014) used coal-based direct reduction to
can be disposed of in a landfill without special treatment. De Andrade achieve the purpose of recovering iron from lead slag. The lead slag was
Lima and Bernardez (2011) tested the leaching toxicity of the lead mixed with coal and calcium oxide at a mass ratio of 50: 15: 5, and was
smelting slag by following the TCLP. The results showed that Pb, Zn, roasted at 1250 °C for 45 min. Under the condition of two-stage
and Cd had a low leaching rate in a weak acid environment and for grinding magnetic separation, an iron grade of 92.75% was obtained
short exposure. In general, short-term leaching tests, such as TCLP tests and a recovery rate of 92.3% was achieved. Wang et al. (2017) studied
(18 h) and the EU standard test EN 12457-2 (24 h), showed that the the recovery of iron, lead, and zinc from lead slag by means of coal-
concentration of most toxic elements in lead slag was lower than the based direct reduction. After the direct reduction, fayalite and magne-
limit value (Table 4) (De Andrade Lima and Bernardez, 2013; Saikia tite in the lead slag were transformed into metallic iron. An iron grade
et al., 2012). However, the long-term slag–water interaction can lead to of 93.73% was obtained and a recovery rate of 80.32% was achieved
a significant increase in the concentration of toxic elements released through magnetic separation. The aforementioned research studies
from the slag compared with that predicted by leaching tests. When the showed that the addition of CaO can reduce the initial temperature of
lead slag was tested by means of a batch leaching procedure that lasted reduction of fayalite (Fe2SiO4) and hercynite (Fe2AlO4) to metallic iron,
for 12 years, Zn was released from lead slag in great amounts, ex- thus promoting reduction reaction. In addition, CaO reacts easily with
ceeding the limit value of the hazardous waste (Ettler and Johan, 2014). Fe2SiO4 and Fe2AlO4 to form CaSiO3 and CaAl2O4, respectively, the
The synthetic precipitation leaching procedure (SPLP) proposed by reactions of which are as follows:
the United States Environment Protection Agency (USEPA) was de-
Fe2SiO4(s) + CaO(s) + 2C(s) = 2Fe(s) + CaSiO3(s) + 2CO(g), (9)
signed to evaluate the effect of lead slag on groundwater and surface
water by simulating the interaction between lead slag and precipitation FeAl2O4(s) + CaO(s) + C(s) = Fe(s) + CaAl2O4(s) +CO(g). (10)
(U.S. Environmental Protection Agency (USEPA, 2008). The leaching
result of SPLP test was compared with drinking water standards A new bath smelting process was developed for the recovery of iron
(Table 4) to assess the elements leaching potentials of lead slag. The from lead slag (Li et al., 2017a, 2017b, 2017c). Under the conditions of
concentration of toxic elements in lead slag following SPLP test ex- reduction temperature of 1575 °C, a C/Fe molar ratio of 1.6, and a
ceeded US EPA standards for drinking water (De Andrade Lima and basicity of 1.2, pig iron with 93.58% Fe was obtained. In the process of
Bernardez, 2011, 2013). direct reduction, the metallization rate reached 99.79% and the iron
recovery rate reached 99.61%. Li et al. (2017a), (2017b), (2017c)
studied the reduction mechanism of the bath smelting process and the
3. Recovery of metals from lead slag
recovery of lead zinc at 1550 °C for 15 min. Moreover, 96.64% of lead
and 99.99% of zinc were volatilized under the best conditions of C/Fe
The valuable metals in lead slag are mainly iron, and a small
molar ratio and basicity, which were 1.8 and 1.2, respectively. The li-
amount of zinc, lead. Various methods of recovering metals from lead
quid iron droplets play a critical role in the reduction of zinc and lead,
slag will be briefly reviewed, focusing on pyrometallurgical, hydro-
the reduction mechanism of which is shown in Fig. 6. The leaching
metallurgical, and bioleaching technology.
toxicity of the treated lead slag is significantly lower than the en-
vironmental limit regulations of USEPA and China, even at pH 1. The
3.1. Pyrometallurgy recovery of lead and zinc from lead slag can contribute to the recycling
of disused resources, as well as to the minimization of their negative
Pyrometallurgical technology is an effective approach to recover effects on the environment.
high content of Fe and of the volatile metals Pb and Zn from primary Lead slag is a solid waste with a high iron content, and iron exists in
lead slag. The average iron concent in the slag is more than 30%; a complex form. Based on the aforementioned results, iron in lead slag
however, it cannot be used directly as raw material for steel mills be- was recovered by direct reduction after magnetic separation. Lead and
cause Pb and Zn in slag are harmful to the iron smelting process. The zinc are effectively volatilized under high temperature reducing con-
iron recovery from lead slag is difficult through the use of conventional ditions. Through the recovery of lead and zinc from lead slag, zinc and
mineral processing methods, whereas iron recovery is feasible via the lead can be resourcefully utilized and environmental problems can be
direct reduction process (Guo et al., 2018). Iron is mainly in the form of solved. Due to the difficulty of reaction control, there are higher re-
fayalite (Fe2SiO4) and magnetite (Fe3O4); therefore, it can be extracted quirements for equipment. In addition, sulfur dioxide is produced in the
as iron concentration via direct reduction followed by magnetic se- reaction process, so the collection and treatment of sulfur dioxide
paration (Li et al., 2012a, 2012b; Yu et al., 2015). Meanwhile, lead should be strengthened. Moreover, pyrometallurgical technology re-
components and zinc compounds are reduced to volatilize into flue gas quires a significant amount of energy for the high temperatures above
in the form of dust by using various types of reductants, such as carbon, 1200 °C; thus, it will consume non-renewable resources of coal, coke,
carbon monoxide, pyrolysis gas, and iron. Therefore, the direct reduc- etc. This technology is more suitable for industrial production, com-
tion and then magnetic separation process is suitable for the treatment bined with electric furnace, fuming furnace, reverberatory furnace,
of lead slag and the recovery of valuable metals. flash furnace, etc. At present, the recovery of metals from lead slag by
Thus far, extensive laboratory research studies have been conducted pyrometallurgical process has been industrialized and achieved certain
and the desired results have been achieved through the use of the direct
144
D. Pan, et al.
Table 3
Phase composition of lead slag.
Group Phases Primary lead slag Secondary lead slag
(Ettler (Ettler and (Seignez (De Andrade Lima (Ettler and (Sobanska et al., (Yin et al., (Kim et al., (Forte (Lassin (Štulović (Shirinbayan et al.,
et al., Johan, 2003) et al., 2006) and Bernardez, Johan, 2014) 2016) 2016) 2017b) et al., et al., 2007) et al., 2013) 2014)
2001) 2011) 2017)
Silicates Fayalite (Fe2SiO4) * * *

Olivine [(Ca,Fe)2SiO4)] * *
Kirschsteinite (CaFeSiO4) *
Hedenbergite(CaFeSi2O6) * *
Willemite (Zn2SiO4) * *
Melilite series * * * *
[Ca2(Fe,Mg,Zn,Al)
(Si,Al)2O7]
Oxides Spinel series (Zn,Mg,Fe) * * * * * *
(Fe,Al,Cr)2O4
145
Franklinite (ZnFe2O4) *
Magnetite (Fe3O4) * * * * * *
Hematite (Fe2O3) * *
Wüstite (FeO) * * * * *
Litharge (PbO) * * *
Sulphides Galena (PbS) * * * * * * *
Pyrrhotite (Fe1–xS) * * * * * * *
Wurtzite (ZnS) * * *
Covellite(CuS) * * *
Anilite (Cu7S4) *
Chalcopyrite (CuFeS2) *
Bornite(Cu5FeS4) * * *
Chalcocite(Cu2S) *
Digenite (Cu9+xS5) * * *
Cubanite (CuFe2S3) *
Marmatite (Zn1-xFexS) *
Metals Metallic lead (Pb) * * * * * * * * *
Copper (Cu) *
Resources, Conservation & Recycling 146 (2019) 140–155
Table 4 PbCl2 was converted to PbCl42− ions as ion-complexing agents by

Limit values for waste acceptance at landfill and drinking water standards. chloride ions. More than 96% of lead was effectively recovered in op-
Limit values Limit values for waste acceptance Drinking water standards timum condition (t = 60 min, T = 80 °C, n = 800 r/min, 200 g/L NaCl,
for waste at landfill in EU (mg/kg) for US EPA (mg/L) 80 g/L FeCl3, L/S = 16).
acceptance at
landfill in US PbS(s) + 2Fe3+(aq) + 2Cl-(aq) →PbCl2(s) + 2Fe2+(aq) +S° (11)
(mg/L)
Non- Inert Non- Hazardous Primary Secondary NaCl(s) → Na+(aq)+ 2Cl-(aq) (12)
hazardous hazardous Drinking Drinking
Water Water PbCl2(s) + 2Cl-(aq) → PbCl42-(aq) (13)
Pb 5 0.5 10 50 0.015 – The process of recovering lead from secondary lead slag by acetic
Zn – 4 50 200 – 5 acid leaching was studied, as shown in Fig. 7 (Forte et al., 2017). Me-
Cd 1 0.04 1 5 0.005 – tallic lead could be dissolved by concentrated acetic acid leaching from
As 5 0.5 2 25 0.01 – the slag. About 95% lead was dissolved, while only 6% iron was dis-
Cu – 2 50 100 1.3 1.0
solved under the optimal condition (T = 25°C, t = 2 h, L/S = 20 mL/g).
Cr 5 0.5 10 70 0.1 –
Hg 0.2 – – – 0.02 – When sulfuric acid was added, the dissolved lead was precipitated into
Ag 5 – – – – 0.1 PbSO4 to recover lead, while the proton in sulfuric acid regenerates
Se 1 0.1 0.5 7 0.05 – acetic acid. Acetic acid could be recovered by distillation and reused in
Ba 100 20 100 300 2 –
a second leaching step. But the disadvantage of this method is that it
Al – – – – – 0.05 - 0.2
Fe – – – – – 0.3
can only recover lead in metal state from lead slag.
Mn – – – – – 0.01 Nitrate-based hydrometallurgical processes have certain uniqueness
and superiority, which can produce high oxidation conditions and is
effective leaching agent for most sulfides (Gok and Anderson, 2013).
economic benefits. A chemical plant in Hunan Province of China re- Shu et al. (2015) used a HNO3-NaCl solution as a leaching liquid to
covered lead and zinc from lead slag and produced lead sulfate pro- transform the lead from the lead slag to the form of [PbCl4]2−, as
ducts. It can make a profit of 900 yuan for 1 ton of lead slag (Li et al., shown in Fig. 8. The lead ions in the filtrate are converted to PbC2O4 by
2012a, 2012b) sodium oxalate; then, a lead oxide powder is obtained via calcination.
Kim et al. (2017a; 2017b) proposed two routes of selective recovery
of lead, copper, nickel and zinc from lead slag. The first route included a
3.2. Hydrometallurgy two-step leaching process, which combined Fe(III)-HNO3 leaching with
roasting and then water leaching, as shown in Fig. 9. In the first step,
With the increasingly strict legislation on the discharge standard of the leaching rate of lead is 90% under the optimum conditions (L/S
pyrometallurgy, increasing attention has been drawn to the recovery of ratio of 8, 0.5 mol L−1 of HNO3, 0.15 mol L−1 of Fe(III), 25 °C). Using Fe
lead slag via the hydrometallurgical process, particularly the secondary (III) as an oxidation agent, the Pb leaching from the matte amounted to
lead slag. The main lead compounds in the secondary lead slag are 90% at 25 °C. The second step was to roast at 600 °C and then leach in
galena (PbS) and metallic lead (Pb). To recover Pb, leaching of galena water at 50 C. This process converted iron sulfide into oxides and se-
and metallic lead has been investigated by many researchers, including lectively leached nickel, copper and zinc.
chloride leaching systems, acetic acid leaching systems, and HNO3- The leaching of lead, copper, nickel and zinc from lead slag in nitric
based leaching systems. acid by one-step oxidation process was studied, as shown in Fig. 10.
Chloride systems can leach galena to form the soluble ionic com- Under the optimum conditions, the leaching rates of lead, copper, zinc
plexes at high brine concentrations. FeCl3-NaCl system was used for and nickel were 92%, 60%, 70% and 66% respectively, while the
recycling Pb from lead slag by Golpayegani and Abdollahzadeh (2017). leaching rate of iron was still very low (2%).
PbS reacted with strong oxidant FeCl3 to form PbCl2. A saturated so- The selective recovery of lead, copper, nickel and zinc by the ion-
dium chloride solution provided a high concentration of chloride ions.
Fig. 6. Reduction mechanism of zinc and lead during iron oxide reduction (Li et al., 2017a).
146
Fig. 7. Flow sheet for the recovery of lead from lead slag by acetic acid leaching (Forte et al., 2017).
exchange adsorption using diethylenetriaminepentaacetic acid (DTPA) comprehensive recovery efficiency of valuable metals in lead slag are
functionalized chitosan-silica hybrid materials was studied. The se- relatively high. However, the waste acid and residue generated in the
paration of zinc, nickel and copper can be achieved by applying the process require further disposal to prevent environmental pollution.
reduced pH gradient, as listed in Table 5.
Hydrometallurgical technology can effectively separate different 3.3. Bioleaching
elements selectively from lead slag by controlling appropriate condi-
tions in aqueous solution. The separation, extraction and Bioleaching is a technology that utilizes microorganisms to convert
Fig. 8. Flow chart of the recovery of lead in an HNO3-NaCl solution (Shu et al., 2015).
147
Fig. 9. Two-step leaching process of Fe (III) -HNO3 leaching (Kim et al., 2017a, 2017b).
solid compounds into recoverable soluble and extractable elements were leached at 65 °C, a pH of 1.5, and at a pulp density of 5%. Guo
(Pollmann et al.,2018). Bioleaching is suitable for slags because its et al. (2010) further optimized the parameters of the pH value, the pulp
advantages include mild reaction conditions, low energy consumption, density, and the particle size that affected the metal leaching in the lead
simple process, and small environmental impact. Silicates and glass slag. Under the optimum conditions of pH 1.5, a pulp density of 10%,
matrix are the main components in lead slag (Piatak et al., 2015). The and slag size of less than 0.83 mm, 86–91% of As, 90–93% of Cu,
dissolution process of silicates and glass matrix is affected by many 90–94% of Mn, and 81–87% of Zn were bioleached after six days.
mechanisms, including acid erosion, the presence of organic and Bioleaching can destroy the amorphous structure of lead slag and can
thermal activation (Potysz et al.,2018). Bioleaching can effectively re- effectively extract toxic elements such as As, Cd, Cu, and Zn. The
cover valued metals (i.e., Cu, Fe) and reduce toxic elements (i.e., As, bacteria eroded the lead slag to form a large number of holes and pits to
Cd) from the primary lead slag (Guo et al., 2008). However, the effi- enhance the leaching of metals, as shown in Fig. 11.
ciency of bioleaching depends largely on the pH, temperature, pulp In the aforementioned research works, the indigenous moderate
density, and leaching time (Halinen et al., 2009; Panda et al.,2015). thermophilic bacteria were used; thermophilic bacteria belong to the
Cheng et al. (2009) studied the feasibility of recovering valued heterotrophic bacteria, which require yeast extract as their energy and
metals and removing toxic elements from the lead slag by bioleaching carbon source, resulting in a high bioleaching cost. Wang et al. (2015)
technology. More than 80% of Al, As, Cu, Mn, Fe, and Zn in lead slag recovered valuable metals and removed toxic elements from lead slag
Fig. 10. One-step leaching process of Fe (III) -HNO3 leaching (Kim et al., 2017a, 2017b).
148
Table 5 requirements of ordinary highway construction. Lead slag can be used

Separating Zn, Ni, and Cu by applying a decreasing pH gradient. as an aggregate in pavement bases, as well as in subbases. Buzatu et al.
pH 1.5 1 0.5 (2015) analyzed the geometrical, physical, and mechanical properties
of lead slag. The lead slag had uniform grain size, good resistance to
Separation of metals Zn Ni Cu shear, and good drainage properties. The internal friction angle of the
granulated lead slag, located between 33.7° and 38.2°, indicated a good
resistance to shear. It was insensitive to the presence of water and it was
by using autotrophic bacteria. The main advantages of autotrophic not porous; therefore, it possessed good drainage properties. Owing to
bioleaching are the cheap energy sources and the low temperature all the aforementioned, lead slag is suitable for use as a road sub-base
(30 °C). The bioleaching is an effective method to extract Zn, Cd, and In material under a waterproof coating.
from lead slag. The results indicated that the extraction rate of Zn, Cd, The assessment of the environmental risk caused by the use of lead
and In were 90%, 86%, and 71%, respectively; however, the extraction slags as construction material is important as well. Barna et al. (2004)
efficiencies of Pb, As, and Ag were poor. evaluated the leaching performance of the road material with lead slag
Bioleaching can be used for the recovery of valuable metals and for by the multi-step European test ENV 12-920. The results showed that
the removal of toxic elements from the lead slag. A high recovery rate of the release of Pb and Zn was controlled by the pH of the leaching so-
metals can be achieved by bioleaching at the laboratory scale, however, lution. The leaching of lead and zinc reached mininum between pH 8
this technology can not scale up to an industrial level due to long and 10. Conversely, for pH higher than 12 and lower than 6, the release
processing time, low processing capacity, and harsh leaching condi- of Pb and Zn increased significantly. Therefore, lead slag is used as road
tions. Another problem is the separation of the metals from the leachate construction material under acidic and alkaline conditions, Pb and Zn
in biological extraction process. Thus, bioleaching is unsuitable for will be released from the road material. Therefore, the environmental
large-scale industrial production. impact of the use of lead slag as a partial substitute of sand in road
construction should be further considered.
4. The utilization of lead slag in construction materials The use of lead slag in road construction replaces natural ag-
gregates, such as sand, which minimize the exploitation of natural re-
4.1. Use of lead slag in road constructions sources. Additionally, it provides ways to reduce the amount of waste,
land occupation, road maintenance and construction costs. Attention
The road construction is divided into the surface layer, the base, and needs to be focused on the long-term environmental impact of the slags
the subbase. In general, cement-stabilized sand is used in the pavement used in road construction. Although lead slag as road material can meet
base. Lead slag is a black granular material similar to sand; it has a high the performance requirements in laboratory research, it is not re-
specific gravity of 3.6–3.9 g/cm3 owing to its high content in iron oxide. commended to use lead slag as road material in real life.
The lead slag has a better granularity and grain size curve compared
with sand (Buzatu et al., 2015). Therefore, the granulated lead slag can 4.2. Use of lead slag in concrete and cement mortar
be used as a substitute for sand and natural aggregates in road con-
struction. Waste slag as an aggregate can consume a significant amount of
Li et al. (2016) selected the lead slag to replace part of sand as waste residue because this is the main component of concrete and ce-
aggregate for road bases. When 15% of lead slag and 5% of cement are ment mortar (Brito and Saikia, 2013; Cardoso et al., 2018; Meng et al.,
used, the compressive strength of road pavement can meet the 2018). Several researchers have investigated the possibility of using of
Fig. 11. SEM images of the lead slag and the residues after six days: (1) lead slag, (2) bioleaching residues after six days, and (3) residues from the abiotic acid
leaching after six days (Guo et al., 2010).
149
primary lead slag and secondary lead slag as fine aggregate and coarse strength, and compressive strength) indicated that cement produced
aggregates in concrete, as well as its effects on the mechanical prop- through the use of lead slag performed better than cement produced
erties of concrete (De Angelis and Medici, 2012; Mosavinezhad and through the use of iron ore. However, lead slag only accounts for ap-
Nabavi, 2012). Atzeni et al. (1996) proved that it is feasible to use proximately 5% of the raw ingredients. In a different study, researchers
granulated primary lead slag in the partial or total replacement of sand used the lead and zinc smelting slag as the ferrous raw material to
in concretes. produce Portland cement, entirely replacing iron ore (Li et al., 2004).
The production of concretes containing granulated primary lead The results showed that the burnability of a mixture of 6% slag had
slag as a substitute for sand mixed in different proportions by 25%, obviously improved. Zn and Pb were fused into Alite and iron phase to
50%, 75%, and 100% by weight of sand have been studied (Alwaeli, improve their activity, which plays the role of mineralization and fu-
2013). The compressive strength of concrete prepared from lead slag sion. Good burnability and fluxing action can effectively reduce the
was superior to that of ordinary concrete. In addition, concrete con- heat consumption. Lead slag can significantly improve the burnability
taining lead slag absorbed gamma radiation more, which made it dif- of raw meal, improve clinker quality, and reduce the consumption of
ferent from ordinary concrete. coal. The utilization of lead slag to produce cement clinker can decrease
Saikia et al. (2012, 2008) used lead slag to replace 25–35% of the the producing-cost of cement about 5%–6% (Dai and Chen, 2010).
fine aggregate in the preparation of the cement mortar. The strength of The toxic elements that appear in the cement matrix interfere with
the cement mortar in which lead slag had been added was lower than the hydration reaction, particularly at the early stages (De Angelis and
that of the control mortar during the first 28 days; however, the Medici, 2012). More specifically, the active centers of dicalcium silicate
strength after the first 90 days exceeded that of the control mortar. were hindered in the hydration, resulting in less silicate minerals; thus,
Cement mortar with added lead slag has been tested according to the the cement was more susceptible to acid attack. Lead was very mobile
EN 12457-2 standard. The leaching amounts of Cu, Pb, and Zn were in the alkaline environment of cement and susceptible to high release
1.31–1.81 mg/kg, 68.5–74.3 mg/kg, and 3.4–4.1 mg/kg, respectively, into the environment. Therefore, only a limited amount of lead slag can
which were higher than the limit values pertaining to the recycling of be incorporated in cement. In addition, China issued “cement kiln co-
waste for use as a construction material in the Flanders region of Bel- disposal of solid waste pollution control standards” and “cement kiln
gium. co-disposal of solid waste environmental protection technical specifi-
The secondary lead slag has been used in a cement-based stabili- cations” to set strict restrictions on the amount of heavy metals added
zation/solidification process for the preparation of concrete (Cioffi into the kiln. The maximum allowable inputs of Pb and Zn is 1590 and
et al., 2000). The addition of up to 30% of lead slag did not affect the 37,760 mg/kg. Therefore, the disposal of lead slag will be limited, the
hydration chemistry of the binder. The unconfined compressive amount of lead slag is about 3–5%. Lead slag can be used as inert
strength of the produced concrete blocks was 23–25.6 MPa. materials in the cement, which requires a careful control or a pre-
Penpolcharoen (2005) used 20% slag as a cement substitute and 100% treatment.
slag as an aggregate substitute to produce concrete blocks with high
compressive strength. 4.4. Use of lead slag in geopolymers
The addition of lead slag to the mortar and the concrete is an effi-
cient method of waste utilization. Additionally, the reuse of lead slag in The geopolymer is an alkali aluminosilicate material produced by
concrete production reduces waste disposal costs and protects the en- the activation of a solid aluminum silicate precursor with better
vironment by conserving large amounts of primary raw materials. strength, durability, and acid resistance than cement-based materials
However, this method fails to achieve the maximum of comprehensive (Yousef et al., 2009). The geopolymers has been used as a matrix for the
utilization of lead slag, because valuable metals such as lead, zinc, solidification/stabilization and immobilization of various types of ha-
copper and iron are still in concrete. On the other hand, the concrete zardous waste, in which toxic elements can be fixed in 3D network
that contains toxic elements may cause potential pollution in the en- geopolymer structures (Toniolo and Boccaccini, 2017). The leaching of
vironment. The chemical resistance and durability of concrete in which lead in the geopolymer can be minimized (van Jaarsveld and van
lead slag has been used needs to be further studied, particularly in Deventer, 1999). Guo et al. (2017) explored the immobilization me-
terms of the corrosion and the leaching process. Atzeni et al., (1996) chanism of lead in geopolymers. Lead compounds were solved in a
studied the leaching behavior in slightly acid and strongly alkaline sodium hydroxide solution, which was then dispersed into the network
environment. The concrete released 228 mg/L Pb and 30 mg/L Zn at of geopolymers; this process ensured physical encapsulation, as well as
pH = 5. The highest concentrations of Pb and Zn were 115 mg/L and chemical bonding. Moreover, Zheng et al. (2015) confirmed the im-
1.2 mg/L in the alkaline environment. Tests carried out on the concrete mobilization of Pb2+, Cu2+, Zn2+, and Cd2+ in geopolymers. In recent
used here suggest that the concrete releases significant amounts of lead years, lead slag containing toxic elements has been incorporated to the
in acid and strongly alkaline environment. This implies that the con- geopolymers.
crete using lead slag cannot be used in acid and alkaline conditions. Primary lead slag contains a great amount of Si and a small amount
of Al. Fly ash becomes with lead slag, which supplements the Al defi-
4.3. Use of lead slag in cement clinker ciency of lead slag. Lead slag can be mixed with alkalis and fly ash, and
it then converts to a geopolymer (Onisei et al., 2012). The preparation
Primary lead slag has a high iron content, which can replace iron process of a geopolymer is shown in Fig. 12. The compressive strength
ore as a raw material to produce cement clinker. In addition, some reaches its maximum value when the addition of lead slag was 70%.
aluminum silicate and zinc silicate form in primary lead slag, and can The bulk density increased with the increase of lead content, while the
contribute to the melting and the mineralization of the raw material water absorption decreased with the increase of lead content. The in-
during the calcining of the raw material (Zhou, 1992; Carvalho et al., organic polymer consisting of 70% lead slag and 30% fly ash had a
2017). During the calcining process of cement clinker, lead slag can water absorption of 19.3 ± 0.7% and a compressive strength of
reduce the melting temperature, promote the calcination, accelerate the 47 ± 4 MPa. The comparison of the leaching results before and after
action of 2CaO·SiO2 and CaO, and can form 3CaO·SiO2; thus, the free polymerization showed that the leaching of lead decreased and the
calcium oxide can be reduced and a better burnability can be obtained leaching of Zn and As increased. This geopolymer had a great influence
(Lan et al., 2004). on the pH in selected cases. Albitar et al. (2015) produced geopolymer
Lin (2000) reported that the primary lead slag was successfully used concrete using lead slag and fly ash. The mechanical properties of the
to replace iron ore as an iron adjustment material in cement clinker geopolymer concrete that had been prepared by using 25% fly ash and
production. The performance testing results (burnability, flexural 75% lead slag as adhesives and 100% lead slag as fine aggregates were
150
Fig. 12. The preparation process of geopolymers.
However, the resources of alkaline activators, such as NaOH and

Na2SiO3, are limited and their cost is higher. Moreover, the negative
effects of production and use of alkaline activators on the environment
affect the popularization and application of this type of materials to a
certain extent.
4.5. Use of lead slag in glass-ceramics
Ceramic and glass technologies are considered feasible for disposing

hazardous wastes because they immobilize the regulated heavy metals
in a stable matrix. In addition, they can be transformed into high value-
added materials with market potential (Pelino, 2000). When the
amount of the glass forming agent (SiO2, Al2O3, and CaO) is suitable for
glass molding, the metallurgical slag can be used as a potential raw
material for the production of glass material (Kritikaki et al., 2016). In
the process of glass melting, harmful elements are chemically combined
in a persistent amorphous network. Therefore harmful metallurgical
slag vitrification is an excellent method for fixing toxic elements
(Pisciella et al., 2001). According to the composition, glass can be
transformed into glass-ceramics with excellent properties by adding
nucleating agent under suitable heat treatment conditions.
The main components of lead slag are SiO2, CaO, and Fe2O3, which
can be used as raw materials for glass-ceramics by adding certain in-
gredients. Glass-ceramics have a good immobilization effect on toxic
elements in the lead slag, and the added value of the product becomes
higher. Therefore, glass-ceramics is one of the best options for the use
and harmless disposal of lead slag. Francis (2004) studied the properties
of glass-ceramics that have been prepared by smelting waste slag via
differential scanning calorimetry (DSC), SEM, transmission electron
microscopy (TEM), XRD, EDS, and the Raman spectra. The mechanism
of the crystallization process has been studied and the feasibility of
preparing glass-ceramics by smelting waste slag was verified. Pan et al.
(2015) used lead slag as the main raw material together with waste
glass and fly ash to prepare a calcium pyroxene glass-ceramic via the
melting method. The glass-ceramic was prepared in different colors by
adding different colorants and it met the standard of the industrial
glass-ceramic. Meanwhile, the leaching toxicity test of the glass-ceramic
was lower than the limit; therefore, the glass-ceramic had a strong
immobilization on toxic elements. Zhang et al. (2015) studied the
Fig. 13. The preparation process of glass ceramics.
preparation of glass ceramics via the melting method and used dan-
gerous solid wastes, such as lead smelting slag, as raw materials. The
similar to the 100% fly ash geopolymer concrete. However, the drying amount of lead smelting slag was 20.0–60.0 wt.%, which indicates that
shrinkage of geopolymer concrete with high lead-slag content was the lead smelting slag has been fully used. The leaching concentration
lower than that of the fly-ash-based polymer concrete. Ogundiran et al. of toxic elements in the glass-ceramic prepared via this method is sig-
(2013) incorporated lead slag and fly ash to geopolymers as activators nificantly lower than the specified value. The synergistic preparation of
using spent aluminum etching solutions (AES). The compressive glass-ceramic from lead slag and waste glass has been proven to be
strength of geopolymers that have been produced via AES (80 MPa after feasible by Pan et al. (2018); the preparation process of glass-ceramics
28 days) was lower than that of the K-silicate solution (100 MPa after is shown in Fig. 13. The glass-ceramics conformed to the standard of
28 days) as an activator. When 10% of fly ash was replaced by lead slag, industrial glass ceramics. When the lead slag content was 50%, the
the compressive strength was not affected. The immobilization of Pb flexural strength reached the maximum value of 131.48 MPa. The
was confirmed via the NEN 12457-4 standard, TCLP, SPLP, and NEN leaching of lead, zinc, and cadmium in the glass-ceramic were lower
7375 leaching tests. than the regulatory limits set by the TCLP test. The leaching con-
The geopolymer can effectively immobilize lead slag and utilize a centrations of Pb, Zn, and Cd in the glass-ceramics were
high volume of lead slag to produce geopolymer concrete materials. 0.031–0.064 mg/L, 1.33–2.18 mg/L, and 0.001–0.004 mg/L. Therefore,
151
through this method, high added value glass-ceramic can be obtained

Application scale
Industrialization
and the toxic elements can be effectively stabilized.
Laboratory
Laboratory
The production of glass ceramics through the use of lead slag in-
volves the utilization of a great amount of lead slag. Meanwhile, the
toxic elements in the lead slag are effectively solidified. Through the
production of glass-ceramics from lead slag, the harmless disposal and
the high value-added resource utilization of lead slag has been
High cost of some reagent; Low energy input; High recovery efficiency
High cost of investment； High energy input; High recovery efficiency
achieved; this is a good idea for the disposal of lead slag.

Low cost of investment; Low energy input; Longer period of operation
5. Limitations and prospects
Through the above discussion, there are two ways to utilize lead
slag: metal recovery and used for construction materials. It is believed
that the environmental, economic and technic feasibilities are the major
factors in deciding the suitable process for utilization of lead slag.
Various methods used for the recovery of metals from lead slag are
compared in Table 6. Pyrometallurgy can recover some metals (i.e., Fe,
Pb, Zn) from lead slag, which can obtain high purity by reduction
roasting. In the pyrometallurgy process, great attention should be paid
to the treatment of waste gas. Despite the greatest improvement in
pyrometallurgical technology, some pollution problems are still un-
Economic feasibility
avoidable. For example, air pollution caused by fine particles PM2.5

and PM10 and release of some toxic gases such as sulfur dioxide should
be considered. Pyrometallurgical technology requires expensive
equipment and consumes a lot of energy, which is not suitable for small
and medium-sized enterprises. There are also limitations of pyr-
ometallurgical technology in recovering single metals from lead slag.
Hydrometallurgical processes may introduce secondary pollutants and
cause problems associated with leaching residue treatment. Almost all
Large amount of wastewater; Large amount of waste residues
hydrometallurgical processes use organic and inorganic acids as

leaching agents to extract valuable metal. The recovery of metal from
lead slag by hydrometallurgical process not only produces waste water,
but also produces a large amount of waste residues after metal ex-
traction. The waste reagents and residues produced in this process in-
evitably increase the environmental risk and the cost of post-treatment.
Fine particles pollution; SO2 pollution
Bioleaching technology can produce safer environmental residues. Al-

though bioleaching is environment-friendly, its commercial application
in metal extraction industry is still limited, owing to its longer period of
operation. Therefore, the economic benefits of bioleaching are cur-
Environmental impacts
rently low.
Environment-friendly
In order to achieve economic and environmental benefits of re-

covering metals from lead slag, there are still some challenges for the
future recycling technology innovation. Future technologies should be
ready for commercialization and suitable for small and medium-sized
Comparison of various methods used for metals recovery from lead slag.
businesses in terms of investment or equipment. Because lead slag is a

complex system, a single technology can not solve all the problems.
Therefore, metal recovery technology should be combined according to
the physical and chemical properties of various lead slags. Future
Species of recovery metals
technologies should focus on higher recovery rate, less pollution and

greater sustainability.
Fe, Cu, Zn, As, Cd
Table 7 provides a short summary of the advantages and dis-

Pb, Zn, Ni, Cu
advantages of these recovery methods. The use of lead slag as a sub-

Fe, Pb, Zn
stitute for natural materials in road construction and concrete brings

many environmental and economic benefits to society. However, there
are concerns that these materials may potentially pollute the environ-
ment due to the presence of toxic elements. Limited by toxic elements,
the utilization of lead slag in cement clinker production is extremely
Hydrometallurgical technology
low. Geopolymer has good stabilization effect on toxic elements in lead

Pyrometallurgical technology
slag. However, the extensive use of alkaline activators limits the large-
Bioleaching technology
scale application of geopolymers. Glass-ceramics as high value-added

Recycling technology
products can not only consume a large amount of lead slag, but also
effectively immobilize toxic elements. High energy consumption in the
preparation of glass-ceramics should be considered.
Complete utilization strategies can be developed for minimizing
Table 6
lead slag. For the utilization of lead slag with poor immobilization of
toxic elements, it is considered that the metal in lead slag should be
152
Table 7
The advantages and disadvantages of various utilizations of lead slag.
Utilizations Utilization rate Advantages Disadvantages
Road constructions 15% Reducing the use of natural resources (sand) Leaching risk of toxic elements in road construction.
Concrete and mortar 20–100% High utilization rate of lead slag Leaching risk of toxic elements in acid and alkaline conditions
Cement clinker 3–5% Improving burnability of cement clinker Low utilization rate of lead slag
Geopolymers 70–100% Good solidification of heavy metals Massive use of alkaline activators
Glass-ceramics 20–60% Good solidification of heavy metals; High added value of products High energy-consumption
recovered firstly. The recovery of metal from lead slag produces eco- (4) Geopolymer prepared from lead slag presents excellent im-
nomic benefits, but also reduces the environmental impacts of lead slag mobilization of toxic elements; nevertheless, the extensive use of
by removing potentially toxic elements. Utilization strategies for the alkaline activators limits its wide application. Glass-ceramics is
residues after metal recovery can also be incorporated into the process. another manner to immobilize toxic elements, which not only
Developing residue to produce building materials will help maximize consumes a lot of lead slag, but also produces high value-added
the utilization of lead slag. Comprehensive resource utilization as far as products.
possible for both metals and non-metals in lead slag should be the target (5) Metal recovery technology of lead slag should be combined ac-
of lead slag utilization in the future. In addition, only through strict cording to the physical and chemical properties of various lead
environmental assessment can lead slag products be popularized and slags, and pay more attention to higher recovery rate, less pollution
applied. Making environmental protection standards related to lead and greater sustainability. Combination of metal recovery and re-
slag utilization technology is the key to achieve the environment- sidue utilization should be the target of lead slag utilization in the
friendly utilization of lead slag. future.
6. Conclusions and.
The disposal of lead slag has attracted extensive attention, which Acknowledgments
may affect the surrounding environment due to possible leaching of
toxic elements into the soil or groundwater. But lead slag may also be a This work is supported by the Guangdong Province Science and
secondary resource because it is rich in calcium, iron and silicon. It is Technology Project (2017B020238001). We also thank the Key
necessary to understand the potential environmental impact of this Laboratory of Solid Waste Reuse for Building Materials (SWR-2016-
material and its role as a valuable resource. In this review, based on the 006) for their assistance in this study.
analysis of the production, composition, and environmental impacts of
lead slag, we summarized the research status of utilization of lead slag. References
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Contents lists available at ScienceDirect

Resources, Conservation & Recycling

A review on lead slag generation, characteristics, and utilization T

indirectly endanger human health. It has been conﬁrmed that people

2. Generation and characteristics of lead slag

2.1. Generation of lead slag

Lead slag is a by-product of lead production process, mainly from

Fig. 4. Phase diagram CaO-FeO-SiO2 system (Sinclair, 2009).

Silicates Fayalite (Fe2SiO4) * * *

Table 4 PbCl2 was converted to PbCl42− ions as ion-complexing agents by

Table 5 requirements of ordinary highway construction. Lead slag can be used

Fig. 12. The preparation process of geopolymers.

However, the resources of alkaline activators, such as NaOH and

4.5. Use of lead slag in glass-ceramics

Ceramic and glass technologies are considered feasible for disposing

through this method, high added value glass-ceramic can be obtained

achieved; this is a good idea for the disposal of lead slag.

5. Limitations and prospects

avoidable. For example, air pollution caused by ﬁne particles PM2.5

hydrometallurgical processes use organic and inorganic acids as

Bioleaching technology can produce safer environmental residues. Al-

In order to achieve economic and environmental beneﬁts of re-

businesses in terms of investment or equipment. Because lead slag is a

technologies should focus on higher recovery rate, less pollution and

Table 7 provides a short summary of the advantages and dis-

advantages of these recovery methods. The use of lead slag as a sub-

stitute for natural materials in road construction and concrete brings

low. Geopolymer has good stabilization eﬀect on toxic elements in lead

scale application of geopolymers. Glass-ceramics as high value-added

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