Waste Management 23 (2003) 933–949

www.elsevier.com/locate/wasman

An overview of recovery of metals from slags

Huiting Shen*, E. Forssberg
Division of Mineral Processing, Luleå University of Technology, S-97187 Luleå, Sweden

Accepted 27 November 2002

Abstract
Various slags are produced as by-products in metallurgical processes or as residues in incineration processes. According to the
origins and the characteristics, the main slags can be classified into three categories, namely ferrous slag, non-ferrous slag and
incineration slag. This paper analysed and summarised the generation, characteristics and application of various slags, and dis-
cussed the potential effects of the slags on the environment. On this basis, a review of a number of methods for recovery of metals
from the slags was made. It can be seen that a large amount of slags is produced each year. They usually contain a quantity of valuable
metals except for blast furnace slag and they are actually a secondary resource of metals. By applying mineral processing technologies,
such as crushing, grinding, magnetic separation, eddy current separation, flotation and so on, leaching or roasting, it is possible to
recover metals such as Fe, Cr, Cu, Al, Pb, Zn, Co, Ni, Nb, Ta, Au, and Ag etc. from the slags. Recovery of metals from the slags and
utilisation of the slags are important not only for saving metal resources, but also for protecting the environment.
# 2003 Elsevier Science Ltd. All rights reserved.

1. Introduction Ferrous slag mainly includes iron slag (blast furnace

slag), steel slag, alloy steel slag and ferroalloy slag. Blast
Various slags are produced as by-products in metal- furnace slag (BF slag) and steel slag make up the major
lurgical processes or as residues in incineration pro- part of ferrous slag. The study and utilisation of BF slag
cesses. According to the origins and the characteristics, and steel slag has a long history. For example, as early
the main slags can be classified into three categories, as in 1880 they were used as a phosphatic fertiliser
namely ferrous slag, non-ferrous slag and incineration (Geiseler, 1996). Today, BF slag and steel slag have
slag. Slags usually contain a quantity of valuable metals. found a wide application, such as cement production,
They are actually a secondary resource of metals, rather road construction, civil engineering work, fertiliser pro-
than an end-waste and have been applied as a resource duction, landfill daily cover, soil reclamation, and so on.
material in many areas. In addition, for some applica- Since BF slag contains little Fe, recovery of Fe from it is
tions, slags have comparable or even better properties not important. However, steel slag is usually subjected
than their competitive materials. The third feature is to metal recovery prior to its application outside the
that some slags contain a notable amount of harmful or iron and steel making process. The iron and steel
heavy metals. The release of these metals may cause industry has applied mineral processing technology to
environmental problems. recover steel scrap (Fe: 90%) and iron oxide concentrate
The conventional method for disposal of slags is (Fe555%) from steel slag and use them as feed materi-
dumping. The increasing dump of slags not only occu- als for sintering, blast furnace and steel making (Huang
pies plenty of land, but also wastes resources and can and Wang, 2001). It was reported that the use of the
potentially have an impact on the environment due to recycled iron concentrate not only saves metal resource,
water pollution. Therefore, it is desirable to recover but also improves the iron and steel making process due
metals from slags and to utilise the slags. to Mn, CaO and MgO contents in the recycled material
(Radosavljevic et al., 1996; Svyazhin et al., 1998; Dol-
gorukov, 1991; Huang et al., 2001). Alloy steel slag and
* Corresponding author. Tel.: +46-920-491313; fax: +46-920-
ferroalloy slag usually contain high amounts of alloy
97364. elements, such as Cr, Ni, Mn, Ti, V, Mo. Recently,
E-mail address: [email protected] (H. Shen). some research work has been done on the treatment of
0956-053X/03/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0956-053X(02)00164-2
934 H. Shen, E. Forssberg / Waste Management 23 (2003) 933–949

the slags, especially on the treatment of stainless steel Hg, Se and Ag) are much lower than the Toxicity
slag and charge chrome slag since the former contains Characteristic Leaching Procedure (TCLP) criterion
expensive metals Cr and Ni and the latter contains high concentrations. The results indicate that the elements
amount of Cr (Kortbaoui et al., 1993; Das et al., 1997; are very tightly bound and not released from the matrix
Choudhury et al., 1996). Some commercial plants for (Proctor et al., 2000). Nowadays almost 100% of BF
treatment of charge chrome slag and stainless steel slag slag is utilised in many areas, such as cement produc-
have been reported in operation (Lopez et al., 1997; tion, road construction, civil engineering work, fertiliser
Salamon, 1995; Khan et al., 2001). production, landfill daily cover, soil reclamation, and so
There are many different non-ferrous slags generated on (Huang and Wang, 2001). Since BF slag contains
from non-ferrous smelters. Perhaps copper slag was little iron (Fe < 2%), recovery of metals from BF slag is
subjected to the most extensive research work with also not important.
a long history of over 100 years (Vircikova and Molnar,
1992). There were numerous reports on recovery of Cu, 2.2. Steel slag
Ni, and Co from copper slag (Ziyadanogullari, 2000;
Barnes et al., 1993; Herreros et al., 1998; Basir et al., Steel slag is produced from Basic Oxygen Furnace
1999). Recently, attention was also paid to the treat- (BOF steel slag) and Electric Arc Furnace (EAF steel
ment of salt slag since the increasing aluminium recy- slag) in the steel making. They are about 10–15% by
cling has caused a rapid increase of toxic salt slag weight of the steel output (Proctor et al., 2000). Each
(Reynolds and Olper, 1990; Unger and Becker, 1992; year, a great amount of steel slag is produced in the
Lopez et al., 1994). Industry now has found methods to different countries, as shown in Table 1.
recycle salts and aluminium scrap from salt slag and
turn this toxic slag into useful materials (Reynolds and 2.2.1. Characteristics of steel slag
Olper, 1990; The Ends Report, 1999; Kirchner, 1991). 2.2.1.1. Chemical and mineralogical composition. The
In addition, recovery of Nb and Ta from tin slag and chemical composition of the steel slags from different
Au and Ag from tin slag and other slags were also sources is shown in Table 2 (Motz and Geiesler, 2001;
reported (Gaballah et al., 1997; Li et al., 1995). Okumura, 1993; Bi and Lin, 1999; Fregeau-Wu et al.,
Incineration slag is a relatively new ever-increasing 1993). The main components in the steel slags are CaO,
slag. Over recent years, several studies have been repor- Fe, SiO2, MgO and MnO. Fe in the steel slags is nor-
ted on the treatment, utilisation and metal recovery mally in the form of steel (7–10%), iron oxide and iron-
from incineration slag, mostly in Germany and Japan bearing minerals. They can be separated from slag by
(Kaulbarsch et al., 1997; Pretz and Meier-Kortwig, applying mineral processing technology and recycled as
2000; Schmelzer et al., 1996; Sakai and Hiraoka, 2000). feed materials for sintering, blast furnace and steel
Incineration slag processing by mechanical separation making. In addition, the high content of CaO, MgO and
can obtain Fe scrap and non-ferrous metals such as Al, MnO in steel slags can be used to substitute for a part of
Cu, Pb, Zn and Ag. This has been applied in industry limestone, dolomite and manganese ore so as to reduce
although only a few papers were reported recently in iron and steel making cost. Some steel slags contain
Germany (Kaulbarsch et al., 1997; Pretz and Meier- higher amount of P2O5 and S than iron concentrate.
Kortwig, 2000). This may affect the direct recycling of the steel slags to
The generation, characteristics and application of the iron and steel making process.
various slags will now be analysed and summarised, The main mineral phases of steel slag are metallic iron,
along with a review of a number of methods for recov- dicalciumsilicate (2CaO.SiO2), dicalciumferrite (2CaO.-
ery of metals from such slags. Fe2O3) and wustite (Motz and Geiseler, 2001). But the
mineral composition and mineral grain size are variable
with chemical composition, cooling way and so on. For
2. Ferrous slag example, slow cooling of a typical BOF slag can produce
larger phase grains than fast cooling (Fregeau-Wu et al.,
2.1. Iron slag
Table 1
Iron slag is generated from Blast Furnace (BF slag) in Production of steel slag in the different countries
the iron production, with 220–370 kg slag per ton of
Country Steel slag (BOF+EAF) Reference
iron being produced (Proctor et al., 2000). The amount
(Million ton)
of BF slag is the largest among the ferrous slags. For
example, In USA and Japan, 13 and 24.3 million tons of Europe 12 Motz and Geiseler (2001)
BF slag were produced each year (Proctor et al., 2000; USA 8 Proctor et al. (2000)
China 14.07 Huang and Wang (2001)
Okumura, 1993). Leaching study shows that the con- Japan 12.6 Okumura (1993)
centrations of elements (including As, Ba, Cd, Cr, Pb,
 H. Shen, E. Forssberg / Waste Management 23 (2003) 933–949 935

Table 2
Chemical composition of steel slag (wt.%)

Country Slag Fetotal CaO MnO MgO SiO2 P2O5 Al2O3 S

Europe BOF slag low MgO content 14–20 45–55 <5 <3 12–18 <2 <3 NR
BOF slag high MgO content 15–20 42–50 <5 5–8 12–15 <2 <3 NR
EAF slag low MgO content 18–28 30–40 <6 4–8 12–17 <1.5 4–7 NR
EAF slag high MgO content 20–29 25–35 <6 8–15 10–15 <1.5 4–7 NR
Japan BOF slag (converter) 17.5 44.3 5.3 6.4 13.8 NR 1.5 0.07
EAF slag (electric furnace oxidation) 15.2 38.0 6.0 6.0 19.0 NR 7.0 0.38
China BOF slag 17–27 34–48 1.5–6 2.5–10 9–15 0.9 0.9–2.8 0.2
USA BOF slag 15–30 40–50 5–10 5–10 10–15 1–3 2 NR

NR=no report.

1993). At higher basicities (CaO/SiO2+P2O5 > 2.5), of steel slags were investigated and compared with those
tricalciumsilicate and lime (CaO) become dominant in of natural aggregates by Geiseler, as shown in Table 4
steel slag (Huang and Wang, 2001). Other minerals (Geiseler, 1996). From Table 4, it can be seen that (a)
reported in steel slag include periclase, manganosite, Fe the density of steel slags is higher than the natural
and Mn monticellite, Mn-cordierite, glass, and (Fe, Mn, aggregates (steel slags contain a high amount of iron),
Mg) oxide solid solution (Radosavljevic et al., 1996). (b) steel slags are a hard material (the compressive
strength is close to granite), (c) the resistance of steel
2.2.1.2. Leaching behaviour of steel slag. The release of slags to impact is approximately the same as the natural
metals or harmful elements from slags will cause envir- aggregates (indicating they are difficult to crush) and
onmental problems such as water pollution and soil finally (d) the Los Angeles test values are also high
pollution, and a toxicological risk to humans through (indicating they are difficult to grind).
the inhalation of small slag particles ( < 10 mm). Proctor Moreover, since steel slags contain some reactive
et al. (2000) recently reported a detailed study on the minerals such as 2CaO.SiO2, 3CaO.SiO2 and free CaO
leaching behaviour of iron and steel slags in the USA, as and MgO, they are a water-hardenable material (Steel
shown in Table 3. From the results, it can be seen that Today and Tomorrow (Japan), 1993; Huang and Wang,
none of the metals (elements) in the leachates exceeds 2001). When steel slags comprise a certain amount of
the TCLP criterion concentrations in the TCLP test. free CaO or MgO, they are not stable in volume due to
Therefore, iron and steel slags should not be considered the hydration of free CaO or MgO (Geiseler, 1996; Ghai
a hazardous waste. Similar results and conclusions were and Noseworthy, 1998; Huang and Wang, 2001).
also reported earlier by Geiseler (1996).
2.2.2. Application of steel slag
2.2.1.3. Technical properties of steel slag. The applica- Steel slag has been applied in many areas, as sum-
tion of slags is closely related with their technical proper- marised in Fig. 1 (Okumura, 1993; Huang and Wang,
ties. These are also the important data relevant to slag 2001; Geiseler, 1996; Svyazhin et al., 1998). Basically,
processing, e.g. for crushing or grinding. Some properties the application can be divided into two parts. One is the

Table 3
Comparison of toxicity characteristic leaching procedure (TCLP) slag leachate concentrations to TCLP criteria

Metal (element) TCLP screening criterion TCLP leachate concentration Exceed criterion?
concentrationa (mg/l)
BF BOF EAF BF BOF EAF

Arsenic 5 0.0048 0.0054 0.011 No No No

Barium 100 1.2 0.88 1.67 No No No
Cadmium 1 0.0054 0.01 0.037 No No No
Chromium (VI) 5 0.026 ND 0.018 No No No
Chromium (total) 5 0.22 0.04 1.0 No No No
Lead 5 ND 0.015 0.063 No No No
Mercury 0.2 ND 0.0005 0.00089 No No No
Selenium 1 ND ND 0.0073 No No No
Silver 5 ND 0.029 0.027 No No No

ND=not detected.
a
From Method 1311 Toxicity Characteristic Leaching Procedure.
936 H. Shen, E. Forssberg / Waste Management 23 (2003) 933–949

Table 4
Technical properties of steel slags, in comparison with natural aggregates

Property Unit BOF slag EAF slag Basalt Granite

Bulk density g/cm3 3.1–3.7 3.2–3.8 2.8–3.1 2.6–2.8

Resistance to impact determined on crushed aggregates (8–12 mm) wt.% 10–26 10–26 9–20 12–27
Absorption of water wt.% 0.2–1.0 0.2–1.0 <0.5 0.3–1.2
Freeze/thaw resistance (particle size < 5 mm) wt.% < 1.0 <1.0 <1.0 0.8–2.0
Los Angeles test (test aggregates: 8–12 mm) wt.% 9–18 8–15 – 15–20
Polished stone value (PSV) 54–57 58–63 45–55 45–55
Compressive strength N/mm2 > 100 >100 >250 >120

Fig. 1. Utilization of steel slag.

direct application of steel slag in the iron and steel 2.2.3. Recovery of metal from steel slag
making process; the other includes recovery of metals As mentioned above, steel slag is usually subjected to
from steel slag and then the application of the remain- metal recovery prior to its application outside iron and
ing steel slag outside the iron and steel making process. steel making process. The methods for slag processing
As shown in Table 2, steel slag contains about 30–50% are different, depending on the cooling method, chemi-
CaO and 3–10% MgO. It can be directly used as a flux in cal and mineralogical composition of steel slag, and its
sintering, blast furnace or steel making process for sub- application. In general, steel slag processing includes
stitution of a part of limestone and dolomite. In this crushing or grinding, screening and magnetic separa-
process, Fe in the steel slag is recovered too. In addition, tion, and sometimes removal of P (Huang and Wang,
the use of steel slag in the iron and steel making process 2001; Radosavljevic et al., 1996; Fregeau-Wu et al.,
can also save manganese ore and improve the process 1993).
because there is some MnO in the steel slag. However,
since some steel slags contain a notable amount of P and 2.2.3.1. Size reduction of steel slag. In order to liberate
S, which are harmful to iron and steel making, and metallic iron and iron-bearing minerals from steel slag
approximately 10–18% SiO2, the amount of direct use of and process steel slag for application, size reduction is
steel slag in the iron and steel making process is limited. necessary. This is achieved in two ways. One is multi-
The other part of steel slag (50–90% of the total steel crushing with crushers. A jaw crusher is generally used
slag) is usually subjected to metal recovery and then for the primary crushing, while a cone crusher, hammer
applied outside the iron and steel making process. crusher or impact crusher is used for the secondary
About 85–100% of annual production of steel slag has crushing. It was reported that a roll crusher is not sui-
been applied now in many countries. Table 5 is an table for this operation (Huang and Wang, 2001).
example of the utilization of converter slag in Japan The other way for size reduction of steel slag is one-
(Okumura, 1993). stage dry autogenous grinding. One advantage is that
 H. Shen, E. Forssberg / Waste Management 23 (2003) 933–949 937

Table 5
Production and utilization of converter slag in Japan (1991)

Utilization Production Ratio of utilization

(
103 t/year) (%)
Unit Metal recovery Road Cement Earth works Fertilizer Others Using in own works Total

103 t/year 195 814 692 3316 124 1080 3960 10,181 9965 102.2
% 1.92 7.99 6.80 32.57 1.22 10.61 38.89 100

one autogenous grinding machine can replace several minerals. In a separation test of an as-received slag,
crushers in multi-crushing so that its operation is sim- 50% of the P reported to the tailings. It was also found
ple. Moreover, the metallic iron product discharged that slow cooling of steel slag promotes mineral grain
from the grinding machine contains Fe as high as 80%. growth and the formation of calcium phosphate which
By autogenous grinding, magnetic separation and occurs as fine-grained crystals associated with the dical-
screening, 8% metallic iron, 4–7% iron concentrate and cium silicate matrix. Hence slow cooling will improve
85% slag product can be obtained (Liu, 1991). the liberation of minerals and the separation process.
About 70% of the P was removed from slow-cooled slag
2.2.3.2. Classification and magnetic separation. The by high gradient magnetic separation.
magnetic separation method is used for separating
metallic iron and iron minerals from steel slag. Com- 2.3. Alloy steel slag
monly-used magnetic machines are cross-belt magnetic
separator, drum magnetic separator and magnetic- Various alloy steel slags are generated in the alloy
pulley separator. To improve magnetic separation effi- steel making processes. Compared with BF slag and
ciency, the classification of steel slag fed to magnetic steel slag, the amount of alloy steel slags is small but
separation is carried out. A single or double-deck they usually contain high amounts of alloy elements,
vibrating screen is used for this process. Screens (includ- such as Cr, Ni, Mn, V, Ti, Mo. Since the amount of
ing bar screen) are also used in the crushing circuit or in stainless steel slag is the largest among the alloy steel
classification of final slag product for different applica- slags and since it contains high content of Cr and a
tions, as shown in Fig. 2 (Huang and Wang, 2001). certain amount of Ni, it is necessary to treat stainless
steel slag prior to its application or landfilling. Recovery
2.2.3.3. Removal of P from steel slag. Since some steel of Cr and Ni from stainlees steel slag is not only sig-
slags contain a notable amount of P (1–3%), it is nificant in economy, but also very important for the
necessary to remove the P to recycle more slag to the environment.
iron and steel making process. The study results repor-
ted by Fregeau-Wu et al. (1993) show that P in steel slag 2.3.1. Chemical and mineralogical composition of
occurs predominantly in dicalcium silicate and to a lesser stainless steel slag
extent in dicalcium ferrite in solid solution. High gradient In the stainless steel production, EAF stainless steel
magnetic separation was used to separate the P-bearing slag and Argon Oxygen Decarburization (AOD) stain-
dicalcium silicate from the iron- and manganese-bearing less steel slag are generated. Table 6 shows the chemical

Fig. 2. Recovery of metal from steel slag and slag processing.

938 H. Shen, E. Forssberg / Waste Management 23 (2003) 933–949

Table 6 Table 8
Chemical composition of stainless steel slags Chemical analysis of leachates, ppm and EC50 values (mg/l)

Component AOD slag Element CrTotal Pb Cd Fe Mn Ni Cu EC50 pH

4 5 6 AOD 4 1.0 < 0.5 <0.1 <0.5 0.5 <0.5 < 0.5 >3000 11.0
5 1.0 < 0.5 <0.1 <0.5 0.5 <0.5 < 0.5 >3000 9.5
CaO 47.60 45.50 45.50 6 1.0 < 0.5 <0.1 <0.5 0.5 <0.5 < 0.5 >3000 10.0
SiO2 31.24 26.32 27.61 Standard <5 <5 <1 – – – – <3000 –
Al2O3 1.66 9.69 1.65
MgO 3.65 7.30 7.30 EC50 is the biotoxicity of a solution determined by luminescence
MnO 1.60 2.06 1.41 bioassay with photobacterium phosphoreum in a Microtox toxicity
FeTotal 1.75 3.50 7.40 analyzer.
Na2O 0.08 0.07 0.03
K2O 0.05 0.05 0.05
CrTotal 3.47 4.28 2.48 calcium-aluminium silicates and free lime and periclase
Cu 0.05 0.05 0.12
except that they contain chrome-nickel-magnesium
Ti 0.13 0.68 0.20
Zn 0.02 0.02 0.03 oxide solution in the form of chromites in which Cr and
Pb 0.05 0.05 0.04 Ni exist (Lopez et al., 1997).
Ni 0.25 0.22 0.45
Cd <0.01 <0.01 <0.01 2.3.2. Leaching behavior of AOD slag
Free CaO 3.21 0.51 0.91
The leaching results in Table 8 show that AOD slag
Loss on ignition – – 7.14
Basicity (CaO/SiO2) 1.52 1.75 1.65 can release a noticeable amount of Cr as high as 1 ppm,
which is close to the standard level 5 ppm. In addition,
AOD slag leachate EC50 value (defined in Table 8)
composition of some AOD slags (Lopez et al., 1997). exceeds the standard level of 3000 mg/l (Lopez et al.,
Compared with steel slag (Table 2), the contents of 1997). Therefore AOD slag might be a hazardous slag.
CaO, Al2O3, MgO and MnO in AOD slag are close to In the AOD processing plants, dust control must be
those in steel slag, but SiO2 is much higher than in steel strict for the dry treatment, and further disposal of
slag. Therefore, the basicity of AOD slag is lower than plant waste water from the wet treatment needs to be
steel slag. Moreover, AOD slag contains much less iron taken into consideration.
than steel slag. Hence recovery of iron from AOD slag
is not important. Perhaps the most important char- 2.3.3. Recovery of metals from stainless steel slag
acteristic of AOD slag is that it contains a high amount It is reported that magnetic separation or gravity
of Cr (2.5–4.3%) and some Ni (0.2–0.45%). separation methods have be used for recovery of Ni and
The mineralogical composition of the AOD slags is Cr from stainless steel slag in some commercial pro-
shown in Table 7. Similar to steel slags, AOD slags also cesses (Lopez et al., 1997). But few detailed papers are
consist mainly of dicalcium and tricalcium silicates, published. It seems that more efforts need to be made

Table 7
Mineralogical composition of AOD slags

AOD slag Element

Ca Si Al Mg Mn Fe Cr and Ni

4 Melilite Silicate Melilite Silicate Chromites Chromites Chromites

Merwinite periclase
C2S
C2S.SiO2
Fluorite
5 Melilite Silicate Melilite Silicate Chromites Chromites Chromites
Merwinite periclase
Ti-Ca-
Oxide
6 Melilite Silicate Melilite Silicate Chromites Chromites Chromites
Merwinite periclase a Fe
C2S MgO.Cr2O3
C2S.SiO2
Calcite
Fluorite

C2S, dicalcium silicate; C3S, tricalcium silicate.

 H. Shen, E. Forssberg / Waste Management 23 (2003) 933–949 939

Table 9
Comparison of chemical composition of charge chrome slag with AOD slag

Slag Component (%) Reference

FeTotal SiO2 CaO MgO Al2O3 Cr

Charge chrome slag FeO: 4.0 27.8 7.0 29.2 23.8 8–12 Choudhury et al. (1996)
Das et al. (1997)
Khan et al. (2001)
Stainless steel slag 3–7 26–32 45–48 3–7 2–9 3–4 Lopez et al. (1997)

for treating stainless steel slag and recovering Ni and Cr Das et al. (1997) used magnetic separation method to
from it. treat a charge chrome slag. The pilot test shows that a
Cr concentrate with grade of 57.1% Cr2O3 and yield of
2.4. Ferroalloy slag 1.5% can be obtained from a charge chrome slag (par-
ticle size: 8 mm) containing 9.3% Cr2O3. A two-step
Ferroalloy slag includes FeMn slag, SiMn slag and magnetic separation is used; dry belt magnetic machines
CrFe (charge chrome) slag etc. Since charge chrome slag (belt width: 381 mm) at 1000 Gauss magnetic intensity
contains high content of Cr, more attention has been are used for the first step and 800 Gauss for the cleaning
focused on the treatment of it and recovery of Cr from step. However, up to date no commercial processes
it. It is estimated that an almost equal amount of slag using magnetic separation method to treat charge
and metals are produced in a charge chrome plant. A chrome slag have been reported.
number of papers have been published describing the Gravity separation method seems relatively more
characteristics of charge chrome slag and the methods for effective for the treatment of charge chrome slag
recovery of Cr from the slag. Recently, some commercial according to some reports. The sink-float test results
plants for recovery of Cr from charge chrome slag in presented by Choudhury et al. (1996) show that it is
India and South Africa were also reported (Khan et al., possible to produce a concentrate of 55% Cr with a
2001; Salamon, 1995; Mashanyare and Guest, 1997). yield of 3% at the crushing particle size of 5 mm from
a charge chrome slag containing 11.5% Cr. Khan et al
2.4.1. Chemical and mineralogical composition of charge (2001) also described the gravity separation process for
chrome slag recovery of Cr from a charge chrome slag of 11.53% Cr.
The main components of charge chrome slag are The slag was subjected to two-stage crushing to reduce
MgO, SiO2, Al2O3, Cr2O3, CaO and FeO. A comparison the size to 10 mm and then screened into 10+1 mm
of chemical composition of charge chrome slag with and 1 mm fractions. The coarse fraction was subjected
stainless steel slag is shown in Table 9. The contents of to jigging and the fine fraction to tabling. The jigging
Fe and SiO2 in the charge chrome slag are similar to produced a product analyzing 59.2% Cr with 6.7%
those in the stainless steel slag. CaO is much lower but yield, while the tabling produced a low grade of con-
MgO and Al2O3 are much higher in the former than in centrate containing 29.2% Cr.
the latter. Charge chrome slag usually contains 8–12% Gravity separation methods for recovering Cr from
Cr, which is higher than in stainless steel slag. There- charge chrome slag have been applied in industry. In
fore, treatment of charge chrome slag is also necessary. South Africa, a charge chrome slag commercial plant
The mineralogical study results by Das et al. (1997) with a capacity to recover 50 kt/a of ferrochrome was
show that the major phases in charge chrome slag are reported in operation in 1995. Jigging was adopted in
spinel and non-crystalline glassy Ca–Mg–Al silicate. The the plant for the coarse fraction (25+1 mm) and
minor phases include olivine, chromite and metallic pha- spiral for the fine fraction (1 mm) (Salamon, 1995). In
ses. The chromite comes from the unreacted chromite ore India, a charge chrome slag and mixed metal commer-
grain. X-ray diffraction (XRD) data and scanning elec- cial plant designed by Svedala was also reported in
tron microscope (SEM) studies indicate that metallic operation in 2000 (Khan et al., 2001).
phases are mainly (CrFe)7C3. Cr appears mainly in chro-
mite and metallic phases. A small amount of Cr is also 2.4.3. Leaching behavior and treatment problems of
found in spinel (Cr2O3: 2–5%) and olive (Cr2O3 < 1%). charge chrome slag
Systematic studies on leaching behavior of charge
2.4.2. Recovery of Cr from charge chrome slag chrome slag have not been reported, but the analysis of
The methods reported for recovery of Cr from charge the water sample from a jigging processing plant of
chrome slag include magnetic separation and gravity charge chrome slag shows that it contains Cr+6 as high
separation. as 1.6 mg/l, which is higher than the level < 0.1 mg/l
940 H. Shen, E. Forssberg / Waste Management 23 (2003) 933–949

stipulated by the World Health Organization for dis- components in the copper slags are Fe and SiO2 with
charge into lakes and rivers (Coetzer et al., 1997). In amount of 25–50% for each. Almost all copper slags
view of this fact, charge chrome slag may be also a contain a considerable amount of Cu (0.5–3.7%) close
hazardous slag and care must be taken for the treatment to or even higher than copper ores. Depending on the
of this slag. Further disposal of the plant water from origins, some slags contain Co and/or Ni at levels wor-
wet treatment is necessary and dust control must be thy of recovery and utilization. Toxic elements (As) and
strict in the dry processes. heavy metals (Pb) exist in some copper slags (see slag 3
and slag 6). Slag 6 is a brass smelting slag quite different
from the ordinary reverbratory and flash slags. It con-
3. Non-ferrous slag tains high Cu and Zn and some Pb.
The mineralogical composition and phase grains
There are a variety of non-ferrous slags produced within copper slags from different origins are quite dif-
from non-ferrous smelters. Extensive studies on metal ferent, depending on many factors such as the type of
recovery from non-ferrous slags have been carried out ores processed, the type of furnaces and the cooling
for the past decades. Most of the studies were on metal methods (Gbor et al., 2000). Slow cooling may result in
recovery from copper slag. Recently, attention was also a significant crystallization of slag components, forming
paid to the treatment of salt slag due to its rapid a large number of different mineral phases. The lower
increase and its serious effect on the environment. There the cooling rate, the larger the mineral phases grow
were also additional reports on recovery of Nb and Ta (Rao and Nayak, 1992). Fast cooling may produce an
from tin slag, Au and Ag from tin slag or other slags amorphous slag and hence the slag is more homo-
and so on. Unlike iron and steel slags, the application of geneous in metal distribution. When copper slag is
non-ferrous slags may cause environmental concerns crystalline, the major phases are usually fayalite along
since they usually contain a notable amount of heavy with other silicates. In most cases Ni and Co are in the
metals or even toxic elements with a relatively high form of oxides (Gbor et al., 2000). Some studies show
solubility (Manz and Castro, 1997; Atzeni et al., 1996). that Co distribution in the slags is very homogeneous.
The reports on the application of non-ferrous slags are However, the forms of Cu minerals are different in dif-
relatively few. ferent copper slags. They may be in the form of oxides
or sulfides or a mixture of them. Copper sulfides are
3.1. Copper slag also different in different copper slags. For instance, slag
1 in Table 10 was reported containing covellite (CuS),
3.1.1. Chemical and mineralogical composition of copper slag 3 containing chalcocite (Cu2S) and metallic copper,
slag Slag 4 containing chalcocite, bornite(Cu5FeS4), metallic
The chemical composition of copper slags from dif- copper, stromeyerite and complex sulphides, and slag 5
ferent origins is shown in Table 10. In general, the main containing bornite and metallic copper.

Table 10
Chemical composition of copper slags

Elements (%) Slag 1 Slag 2 Slag 3 Slag 4 Slag 5 Slag 6 Slag 7

Cu 2.60 0.58 3.70 1.22 2.75–3.30 20.7 0.6–3.2

Co 0.36 0.21 0.25 NR 0.5–0.7 NR NR
Ni 0.045 0.57 NR NR 0.9–1.2 NR NR
Ag (ppm) NR NR 2 NR NR NR NR
Pb NR NR 0.18 NR NR 1.33 NR
Zn 0.425 NR 0.44 NR NR 11.35 NR
Fe 52.0 38.6 49.99 32.24 45–48 NR 32.7–37.3
SiO2 NR Si: 17.40 22.45 NR 24–26 NR 32.5–37.3
Al2O3 NR Al: 2.51 1.14 NR NR NR 2.4–4.0
CaO NR Ca: 1.11 NR NR NR NR 1.8–7.5
MgO NR Mg: 1.65 NR NR NR NR 1.6–4.0
Mn NR 0.03 NR NR NR NR NR
Ti NR 0.15 NR NR NR NR NR
S 4.90 0.93 1.56 NR NR NR 0.5–1.0
As NR NR 0.05 NR NR NR NR

Slag 1: Converter slag from Ergani Mining Co., Turkey (Altundogan and Tumen, 1997). Slag 2: Slow–cooled slag from INCO’s flash smelting
furnace in Sudbury, Ontario, Canada (Gbor et al., 2000). Slag 3: Converter slag from Mount Isa copper smelter, Australia (Barnes et al., 1993). Slag
4: Reverberatory slag from Refimet Division, Chile (Herreros et al., 1998). Slag 5: Converter slag (CS(iii)) from Ghatsila copper plant, India (Rao
and Nayak, 1992). Slag 6: Brass smelting slag from EI–Maady Co. for Engineering Industries, Cairo, Egypt (Basir et al., 1999). Slag 7: Copper slag,
Czechoslovakia (Vircikova and Molnar, 1992). NR: no report.
 H. Shen, E. Forssberg / Waste Management 23 (2003) 933–949 941

3.1.2. Methods for metal recovery from copper slag

A number of methods for metal recovery from copper
slag were reported. Basically, they can be classified into
three categories, namely flotation, leaching and roasting.
Barnes et al. (1993) described an industrial flotation
process of the copper slag at Mount Isa Mines Limited.
The slag is ground to 80%74 mm prior to flotation.
Using sodium sec-butyl xanthate as collector, MIBC as
frother and hydroxy ethyl cellulose as depressant of
magnetite, the process produces a concentrate grading
42.54% Cu with a recovery of 82% from the slag of 3.7%
Cu. But most of Co is reported to the flotation tail. A
similar result was reported by Rao and Nayak (1992). In
the flotation experiment of a converter slag (3.7% Cu, Fig. 3. Effect of H2O2 addition on extraction of Cu, Zn and Pb from
brass smelting slag in HCl leaching.
cooled in a refractory lined pit) with potassium amyl
xanthate as collector, pine oil as frother at pH 8–9, a
concentrate containing 44% Cu was obtained with 96
recovery. Co and Ni were also reported in tailings.
In principle, copper slag flotation is the same as sul-
fide ore flotation. This means only metallic Cu and sul-
fide minerals can be floated effectively. Since Cu in some
slags is in the form of oxides and Co and Ni are usually
in the form of oxides (Co is in homogenous distribution),
the flotation method will not be effective for recovery of
Co, Ni and oxide Cu. Therefore, the application of flo-
tation in copper slag processing could be limited.
Leaching is another method for extraction of metals
from copper slags. The leachants applied in slag leach-
ing include sulfuric acid, hydrochloric acid, ferric chlo- Fig. 4. Effect of H2O2 addition on extraction of Cu, Zn and Pb from
ride, ammonia, cyanide and so on (Basir et al., 1999; brass smelting slag in NH4OH leaching.
Anand et al., 1980). Cyanide was used in the early time,
but was replaced by other leachants due to environ- metals in various forms in slag are reduced into free
mental problems. To increase leaching efficiency, some metals. Then flotation or leaching is used for separation
measures, such as addition of H2O2, pressure leaching of the metals from the slag (Vircikova and Molnar, 1992).
or leaching in Cl2/Cl system, were taken. For example, A more simple and effective method is called sulfating
in the leaching of a brass smelting slag containing 6.3% roasting, in which Cu, Co and Ni in various forms are
Cu (free metal), 14.4% Cu (oxide form), 11.35% Zn converted into soluble sulfates through a series of chemi-
(oxide form) and 1.33% Pb (oxide form) with hydro- cal reactions at 200–600 C by addition of sulfide or sul-
chloric acid or ammonia, addition of H2O2 greatly fate agents (Tumen and Bailey, 1990; Hamamci and
increased the extent of metal extraction, especially in the Ziyadanogullar, 1991; Ziyadanogullarii, 1992, 2000;
hydrochloric acid leaching, as shown in Figs. 3 and 4 Altundogan and Tumen, 1997). Then the soluble sulfates
(Basir et al., 1999). It was reported that by pressure are dissolved in water and separated from the slag. The
leaching with dilute sulphuric acid about 90% Cu and sulfide and sulfate agents used in the roasting include
more than 95% each of Ni and Co could be extracted H2S, H2SO4, (NH4)2SO4, Fe2(SO4)3xH2O and pyrite. The
with only 0.8% extraction of Fe from a copper con- chemical reactions in the sulfurization process with H2S
verter slag containing 4.03% Cu, 1.98%Ni and 0.48% summarized by Ziyadanogullari (1992) are shown below:
Co (Anand et al., 1983). Cl2/Cl (from reaction of
) 3Fe2þ þ S þ 4H2 X
Fe3 X4 þ H2 S þ 6Hþ * ð1Þ
NaOCl and HCl) leaching method was adopted for
extraction of Cu from the reverberatory and flash fur-
Cu2 O þ H2 S *
) Cu2 S þ H2 O ð2Þ
nace slags containing metallic Cu and Cu sulfide miner-
als and complex sulfides with very small size, mainly
2Cu þ H2 S þ 1=2O2 *
) Cu2 S þ H2 O ð3Þ
5–10 mm. Extraction of 75 to 80% Cu and 5% Fe were
obtained at room temperature (Herreros et al., 1998).
Co3 X4 þ 4 H2 S *
) 3 CoS þ S þ 4 H2 X ð4Þ
The objective of roasting is to convert the metals in
copper slag into a desired form which can be separated
from the slag. One way is reduction roasting, in which where X=O2 or SiO2
3 .
942 H. Shen, E. Forssberg / Waste Management 23 (2003) 933–949

The sulfides Cu2S and CoS are then converted into waste (Lopez et al., 1994). Treatment of salt slag is
soluble CuSO4 and CoSO4 during roasting at important not only for the environment, but also for
600–700 C. Ziyadanogullari (2000) used a sulfating reduction of landfilling cost for the secondary aluminum
roasting method to treat a converter slag containing industry (The Ends Report, 1999; Reynolds and Olper,
2.4% Cu, 0.38% Co, 50.3% Fe and 2.92% S. By sul- 1990).
furization in a closed system at 130  C for 1 h with (6.1 Study on the utilization of salt slag began in the
g H2S+25 g H2O)/100 g slag, and then by roasting at 1970s. It was reported that in 1977 a company called
600 C for 6 h, the amounts of Cu and Co dissolved in Engitec designed and installed the first generation salt
water were 99.2 and 98.8%. recovery system at Carisio, Italy (Reynolds and Olper,
In fact, the chemical reactions in the roasting process 1990). In 1986, a more versatile commercial plant devel-
with the addition of Fe2(SO4)3x.H2O (or H2SO4 and oped by B.U.S (Berzelius Umwelt Services AG) in Ger-
(NH4)2SO4) are different from the above. There are not many for recovery of aluminum scrap and salts and
sulfurization reactions in this process. The function of treatment of the noxious gases from salt slag was repor-
Fe2(SO4)3xH2O is to generate SO3 which can react with ted in operation (Beckmann, 1991; Unger and Beck-
metal oxides to produce sulfates when it decomposes mann, 1992). Nowadays, most commercial plants use the
above 480 C. A series of chemical reactions described methods similar to the B.U.S process (Metal Bulletin,
by Altundogan and Tumen (1997) are shown as follows: 1997; Kirchner, 1991; Reynolds and Olper, 1990)

Fe2 ðSO4 Þ3 *
) Fe2 O3 þ 3 SO3 ðor SO2 þ 1=2 O2 Þ ð5Þ 3.2.1. Chemical and mineralogical composition of salt
slag
M þ 1=2 O2 *
) MO ð6Þ
Tables 11 and 12 show the chemical and mineralogical
MS þ 3=2 O2 *
) MO þ SO2 ð7Þ composition of a salt slag respectively (Lopez et al.,
1994). From the results, it can be seen firstly that the
MO þ SO3 *
) MSO4 ð8Þ salt slag contains Al as high as 24.08%, but with only
7.25% in the form of Al metal. The other is in the form
of Al-compounds, including MgO.Al2O3, Al2O3, and a
2MO þ SO3 *
) MOMSO4 ð9Þ
small amount of AlN, Al4C3 and Al2S3 etc. This means
that the maximum yield of recovering aluminum scrap
MO þ Fe2 O3 *
) MOFe2 O3 ð10Þ
from the salt slag by mechanical separation is only
7.25%. Secondly, the results show that approximately
where M=divalent metals. 50% of salt slag is made up of water-soluble minerals.
It was reported by Hamamci and Ziyadanogullari They are halite (NaCl) and sylvite (KCl) and a small
(1991) that H2SO4 is better than (NH4)2SO4 as a sul- content of aluminum nitride (AlN), aluminum carbide
phating agent for roasting of a converter slag containing
2.56% Cu, 0.22% Co and 49.0% Fe. Under the condi- Table 11
Chemical analysis of salt slag
tion of roasting at 200 oC for 60 min with 1.5 times the
stoichiometric amount of H2SO4, Cu and Co recoveries Element Al Na K Si Mg Ca N C Fe S
were 82 and 96% respectively.
wt.% 24.08 21.89 7.47 3.69 2.83 1.07 0.71 0.60 0.50 0.13

3.2. Salt slag

Salt slag is generated from the secondary aluminum Table 12

Mineralogical composition of salt slag
industry. During the smelting process of recycled alu-
minum scraps in reverberatory or rotary furnace, fluxes Mineral wt.%
consisting of NaCl and KCl are added on the molten Al metal 7.25
bath to prevent metal oxidation and remove impurities AlN 2.10
from the charge, and thus salt slag is formed. Approxi- Al4C3 2.40
mately 0.5 tons of salt slag arises when producing one Al2S3 0.20
ton of secondary aluminum (Kirchner, 1991; Lopez et MgO.Al2O3 16.59
Al2O3 7.68
al., 1994). Over recent years, the increasing aluminum b–CaO.SiO2 2.68
recycling has caused a rapid increase of salt slag. SiO2 1.85
Salt slag contains a great amount of water-soluble Na2O.SiO2 4.30
compounds. When salt slag contacts rainfall or K2O.SiO2 0.48
groundwater, it will release chlorides into the water and NaCl 41.92
KCl 4.66
give off noxious gases including H2, NH3, CH4, H2S and Fe–Si 0.75
PH3. It has been classified as a toxic and hazardous
 H. Shen, E. Forssberg / Waste Management 23 (2003) 933–949 943

(Al4C3) and aluminum sulphide (Al2S3) etc. Thirdly, the (b) leaching (c) solid liquid separation (d) gas treatment
remaining part of the salt slag is shown to be mainly and (e) evaporation and crystallization (Beckmann,
non-soluble Al, Mg, Ca and Si oxides, including cor- 1991; Unger and Beckmann, 1992).
undum (Al2O3), spinel (MgO.Al2O3), quartz (SiO2) and
calcium silicate (b-CaO.SiO2). 3.2.3.1. Metal separation. The first step is a dry separa-
tion of metallic Al from oxides and salts. Al metal is
3.2.2. Leaching behavior of salt slag ductile, but oxide and salt aggregates are brittle. Utiliz-
Since salt slag contains a large amount of NaCl and ing this difference, multi-stage crushing and screening
KCl, it will release the chlorides into water when it are used to separate the Al metal from the oxides and
contacts waterfall or groundwater. In addition, metallic salts, as shown in Fig. 5. Through this separation, clean
aluminum and some aluminum compounds in the salt Al metal pieces with approximately 7% yield can be
slag can react with water and give off noxious gases, as obtained from salt slag.
shown below (Reynolds and Olper, 1990): Since this is a dry process, dust control is important.
Dust collection points are designed at all openings,
keeping the machines under negative pressure. The air is
Al þ 3 H2 O ¼ AlðOHÞ3 þ3=2 H2 " ð11Þ passed through a bag collector to capture any dust
before venting.
AlN þ 3 H2 O ¼ AlðOHÞ3 þNH3 " ð12Þ
3.2.3.2. Leaching. The oxide and salt powder from the
Al4 C3 þ 12 H2 O ¼ 4 AlðOHÞ3 þ3 CH4 " ð13Þ first step is then subjected to leaching with water. The
oxides are not soluble while the salts will be dissolved
AlP þ 3 H2 O ¼ AlðOHÞ3 þPH3 " ð14Þ into water. This makes it possible to separate the salts
from the oxides.
Al2 S3 þ 6 H2 O ¼ 2 AlðOHÞ3 þH2 S " ð15Þ
3.2.3.3. Solid liquid separation. After dissolution of the
Therefore, direct landfilling of salt slag may cause salts in the oxide and salt powder, the solid–liquid mix-
serious environmental problems. Accordingly, the cost ture is pumped to a thickener. The underflow of the
of landfilling salt slag is high, for example, £30–35 per thickener is filtered and washed with recycled water.
ton in the UK (Metal Bulletin, 1997). Thus, treatment Then the clean oxides are available for sale or further
and utilization of salt slag is important not only for processing. The overflow of the thickener and the fil-
environmental protection and resource recovery, but tered water are salt-rich solution (brine) which is sent to
also for reduction of landfilling cost for the secondary evaporation and crystallization step.
aluminum industry.
3.2.3.4. Gas treatment. In the leaching, thickening and
3.2.3. Treatment and utilization of salt slag filtering processes, noxious gases are generated. They
The treatment and utilization of salt slag consists of must be captured, diluted to eliminate explosion risk
three parts, i.e. recovery of Al metal, recovery of salts and then treated to remove the noxious constituents.
and further processing of the remaining oxides. As In the B.U.S process, the gases are passed through a
mentioned above, the method used in most commercial scrubber to remove the particulates. Then the clean
plants now is similar to the B.U.S process. It is com- gases are sent through a chemical column with sulfuric
prised of five major steps, namely (a) metal separation acid to remove ammonia. The remaining gases are then

Fig. 5. Separation of metallic Al from salt slag.

944 H. Shen, E. Forssberg / Waste Management 23 (2003) 933–949

Table 13
Variation in contents of Al component with calcinations temperature

Component (wt.%) Temperature ( C)

500 700 1000 1200 1300 1500

Al metal 3.70 2.70 1.50 0.95 0.90 0.90

g–Al2O3 20.37 24.66 9.25 5.45 0.38 0.38
a–Al2O3 20.92 27.69 46.50 47.48 55.79 53.60
Al2O3.MgO 25.74 25.74 30.42 31.59 30.42 31.59
Al2O3Totala 67.30 70.40 76.20 77.30 77.30 76.60
Al4C3 1.40 0.60 0.40 0.18 0.16 0.064
Al2S3 0.19 0.20 0.06 0 0 0
AlN 0.36 0.30 0.10 0.07 0.05 0.04
a
Al2O3Total=g–Al2O3+a–Al2O3+alumina in Al2O3.MgO.

passed through a multi stage absorber to remove other foundry and steel mixes, refractory, mineral wool,
noxious gases. In some other plants, the noxious gases abrasives and ceramic fibres.
are burnt in an afterburner.
3.3. Other non-ferrous slags
3.2.3.5. Evaporation and crystallization. The clear salt
brine from the thickener and filter is boiled in a Recoveries of metals from other non-ferrous slags
multi-effect evaporator in which water is boiled away were also reported. One example is the recovery of Au
and NaCl and KCl crystals grow from the resulting and Ag from a pyrite slag or tin slag. The methods
saturated solution. Finally, a salt product with a reported for Au and Ag recovery from the slags are
yield of about 50% can be produced from the salt similar to those for treating copper slags above, includ-
slag. ing flotation or roasting (Li et al., 1995).
In general, most salt slag processing plants did not Another example is the recovery of Nb and Ta from a
report the further treatment of the remaining oxides. tin-slag reported by Gaballah et al. (1997), as summar-
Only some laboratory results were reported. For exam- ized in Fig. 6. Before chlorination, Fe, Ca, Mn, and Al
ple, Lopez et al. (1994) used calcination to treat the etc. are removed from the tin slag by leaching (acid or
leaching residue of salt slag. By calcination at high successive acid and basic). Then, the Nb and Ta con-
temperature, most Al and its compounds in the residue centrate is subjected to chlorination at 500–1000  C for
are converted into a-Al2O3 and Al2O3.MgO, as shown 24 h with (Cl2+N2) or (Cl2+CO+N2). Nb and Ta
in Table 13. It was estimated that the calcination pro- oxides in the concentrate are converted into volatile Nb
duct can be applied in fused grain, cement and glass, and Ta chlorides and hence they are separated from the

Fig. 6. Recovery of Nb and Ta from tin slag.

Table 14
Chemical composition of the tin slag and leaching concentrates (wt.%)

Sample Nb2O5 Ta2O5 SiO2 CaO FeO Al2O3 SnO2 MnO K2O TiO2 H2O

Slag 5.2 7.5 41.9 11.6 3.3 11.2 0.7 3.7 1.4 1.3
0
LGCa 6.3 13.7 43.3 9.8 2.5 5.2 0.9 2.3 0.8 1.2
5
HGCb 28.0 31.1 10.0 0.6 0.2 0.6 0.2 0.0 0.4 1.4
20
a
Low–grade concentrate.
b
High–grade concentrate.
 H. Shen, E. Forssberg / Waste Management 23 (2003) 933–949 945

Table 15
Results of chlorination of the Nb and Ta concentrates

Concentrates Chlorination with Cl2+N2 Chlorination with Cl2+CO+N2

Nb and Ta Purity of Nb and Conditions Nb and Ta Purity of Nb and Conditions

recovery (%) Ta product recovery (%) Ta product

LGC Nb: >95 Ta: >95 Not high, contaminated by 1000 C, 24 h Nb: >95 Ta: >95 Not high, contaminated by 1000 C, 24 h
chlorides of Fe, Mn, etc. chlorides of Fe, Mn, etc.
HGC Nb: 84 Ta: 65 Pure 1000 C, 24 h Nb: 100 Ta: 100 Pure 4500 C 24 h

residue. The chemical composition is shown in Table 14 Table 16

Composition of MSWI residues
and the results of chlorination are summarized in
Table 15. It can be seen that the optimum combination Component Unit Bottom ash Fly ash
is the chlorination of high grade concentrate (HGC) Si g/kg 210–290 95–190
with (Cl2+CO+N2) at temperature 4500 C for a Al g/kg 47–72 49–78
reaction time of 24 h. Fe g/kg 27–150 18–35
Ca g/kg 65–97 74–130
Mg g/kg 7.7–19 11–19
K g/kg 9.2–22 23–47
4. Incineration slag Na g/kg 22–41 22–57
Ti g/kg 3.2–7.2 7.5–12
With an increase in municipal solid waste (MSW) and S g/kg 1.3–8 11–32
landfill cost, more and more MSW is treated by incin- Cl g/kg 1.2–3.2 45–101
eration. For example, in Switzerland, Japan, Germany, P g/kg 2.9–13 4.8–9.6
Mn g/kg <0.7–1.7 0.8–1.7
France, Sweden and Denmark, 50% or more of the Ag mg/kg 4.1–14 31–95
unrecycled waste is being or will be incinerated (Hjel- As mg/kg 19–80 49–320
mar, 1996). Incineration reduces the volume of the Ba mg/kg 900–2700 920–1800
waste by approximately 90% and allows for recovery of Be mg/kg Nd Nd
much of energy bound in the waste. But when inciner- Cd mg/kg 1.4–40 250–450
Co mg/kg <10–40 29–69
ating 1 ton of MSW, 300–350 kg incinerator bottom Cr mg/kg 230–600 140–530
residue, 0–35 kg filter dust and 5–40 kg residue from Cu mg/kg 900–4800 860–1400
flue-gas purification system are produced (Schmelzer, Hg mg/kg <0.01–3 0.8–7
1995). The increasing incineration of MSW will produce Mo mg/kg 2.5–40 15–49
a considerable amount of MSW incineration (MSWI) Ni mg/kg 60–190 92–240
Pb mg/kg 1300–5400 7400–19000
residues which must subsequently be utilised or land- Se mg/kg 0.6–8 6.1–31
filled. For instance, in Japan and Germany, 6 and 3 Sn mg/kg <100–1300 1400–1900
million tons of MSWI residues are produced respec- Sr mg/kg 170–350 <80–250
tively each year (Sakai and Hiraoka, 2000; Pretz and V mg/kg 36–90 32–150
Meier-Kortwig, 2000). Over recent years, several studies W mg/kg <20–50 Nd
Zn mg/kg 1800–6200 19000–41000
have been reported on the treatment, utilisation and PAH mg/kg 0.23–2200 30–110
metal recovery from MSWI slag, mostly in Germany CB mg/kg 6.7–45 50–890
and Japan. PCB mg/kg <40 <40
CP mg/kg 16–34 120–1800
4.1. Characteristics of MSWI residue PCDD mg/kg 0.2–10 115–140
PCDF mg/kg 0.44–4.5 48–69
TCDD mg/kg 0.02–0.22 1.5–2.5
Depending on the MSW incinerated, the composition TOC g/kg 4.8–13 4.9–17
of MSWI residues varies with the origins. Hjelmar LOI g/kg 5.9–50 11–45
(1996) summarised the ranges of composition of some
TCDD: toxicity equivalents determined according to Eadon’s method.
MSWI bottom ash (excluding the scrap metal portion
Nd: no data available. PAH: polycyclic aromatic hydrocarbons. CB:
and the size fraction larger than 45 mm) and fly ash, as chlorobenzenes. CP: chlorophenols. PCDD: polychlorinated dibenzo-
shown in Table 16. From the results, it can be seen that p-dioxins. PCDF: polychlorinated dibenzofurans. TOC: total organic
in the incineration process Fe and Cu mainly remain in carbon. LOI: loss on ignition (550 C).
946 H. Shen, E. Forssberg / Waste Management 23 (2003) 933–949

the bottom ash, whereas the volatile elements such as needs special treatments, such as vitrification by re-
Cd, Hg, As, Pb and Zn are enriched in the fly ash. In melting and extraction using acid or other solvents. For
addition, fly ash contains more PCDF, PCDD, CP and bottom ash, two disposal strategies were reported. In
CB and has a higher TCDD than bottom ash. Disposal the first, it is processed mechanically and then used, for
of bottom ash is considered less problematic than dis- example, in the construction of streets, roads, and dams.
posal of fly ash. The potential recycling metals in the In the second, more secure treatment, it is pre-processed
bottom ash include Fe (27–150 g/kg), Al (47–72 g/kg), mechanically and then treated with vitrification in which
Cu (0.9–4.8 g/kg), Pb (1.3–5.4 g/kg), Zn (1.8–6.2 g/kg), the organic contaminants are destroyed and inorganic
Ti (3.2–7.2 g/kg), Sn (0.1–1.3 g/kg) and so on. contaminants are stabilised, namely by binding into
The material characterization study by Pretz and mineral matrix and by evaporation and collection in a
Heier-Kortwig (2000) shows that MSWI slag contains highly concentrated form as ‘‘vitrification fly ash’’. The
85–90 wt.% mineral fraction, 1–5 wt.% non-incinerated re-melted slag is used as a resource. In both treatments,
matter and 7–10 wt.% scrap metal. The mineral fraction metal recovery from bottom ash is performed in the
consists mainly of glass, ceramic, porcelain and heating mechanical processing stage. Metal recovery from vitri-
fuel ash, besides relatively large lumps of slag and fication fly ash has also been reported.
building rubble such as concrete, bricks and stones. Schmelzer (1995) reported a process for metal recov-
Partly or non-incinerated material comprises paper, ery from incineration bottom ash, as shown in Fig. 7.
wood, plastic and textile components. The scrap metal The pilot operation results show that 62.6 wt.% pro-
includes non-ferrous and ferrous (Fe) metals, such as tin cessed ash, 35.5 wt.% magnetic material and 1.9 wt.%
plate, aluminium, copper, brass, oil filter and water non-ferrous material can be obtained from the bottom
taps. The thermal conditions during incineration lead to ash. The magnetic material contains 20–30% Fe. After
a complete or partial melting and even to an oxidation further processing with impact crushing, screening and
of the metal components. Surface intergrowth of melted wet magnetic separation, fine scrap with 90–95% Fe
piece of scrap metals with mineral components are also and iron concentrate with 50–55% Fe were produced.
observed. The non-ferrous material mainly comprises Al, Cu, Zn
Incineration residues not only contain high content of and other metals. By further wet gravity separation,
heavy metals, but also can release the heavy metals into light product containing 95% Al and heavy product
water when water leaches through the residues, espe- with Cu 52.1–61.2%, Zn 25.2–36.5%, Pb 1.2–3.5%,
cially through incineration fly ash (Rhyner et al., 1995; Sn 0.67–1.46% and Ag 0–2.0% were obtained
Sakai and Hiraoka, 2000; Hjelmar, 1996). In Japan, fly (Schmelzer et al., 1996).
ash is classified as ‘‘general wastes requiring special A wet treatment reported for recovery of Pb and Zn
controls’’ (Sakai and Hiraoka, 2000). Therefore, further from vitrification fly ash is shown in Fig. 8 (Sakai and
treatment is necessary for incineration residues, parti- Hiraoka, 2000). The fly ash is mixed with acid solution.
cularly for fly ash. Zn and Cu are dissolved into the solution and sepa-
rated from non-soluble Pb by filtration. Then, Zn and
4.2. Recovery of metal from MSWI slag Cu are changed into hydroxide through neutralization
and sulphured. After that Zn cake is obtained by fil-
Recovery of metals from MSWI residues closely tration again. By this treatment, lead and zinc cakes
depends on the characteristics of MSWI residues and grading about 35% Pb and 31% Zn, respectively, are
the disposal strategy for MSWI residues. Since fly ash produced from a vitrification fly ash containing 3.14%
has high heavy metal and dioxin concentrations, it Pb and 6.86% Zn.

Fig. 7. Recovery of metals from incineration residue.

 H. Shen, E. Forssberg / Waste Management 23 (2003) 933–949 947

Fig. 8. Pb and Zn separation and recovering process.

5. Conclusions released. It seems that more research work needs to be

done for the treatment of this slag.
(1) A large amount of various slags are produced as by- Charge chrome slag is one of the ferroalloy slags.
products in metallurgical processes or as residues in More attention is focused on this slag since it contains
incineration processes. According to the origins and the high content of Cr, usually 8–12%. Like stainless steel
characteristics, the main slags can be classified into three slag, it also can release Cr into water and it may be harmful
categories, namely ferrous slag, non-ferrous slag and to the environment. Magnetic separation method was used
incineration slag. They usually contain a quantity of for recovery of Cr from the slag, but up to date there has
valuable metals except for BF slag. Recovery of metals been no commercial application. Gravity separation seems
from the slags and uitilization of the slags not only can more effective for separating Cr from this slag and it has
save metal resource, but also can protect the environment. been applied in industry in India and South Africa.
(2) Ferrous slags mainly include iron slag, steel slag, (3) Non-ferrous slags usually contain heavy metals or
alloy steel slag and ferroalloy slag. Iron and steel slags even toxic elements with a relatively high solubility.
have comparable or even better properties than their There are relatively few reports on the application of
competitive materials for a range of applications. The non-ferrous slags. The main work was focused on
metals in iron and steel slags are tightly bound to the recovery of metals from the slags. Among the non-fer-
slag matrix and not readily leached, and there are few rous slags, copper slag was subjected to the most exten-
environmental concerns regarding their application. sive research work with a history of over 100 years. By
They have been applied in many areas. BF slag contains using flotation, leaching or roasting, it is possible to
little metal and recovery of metal from it is not impor- recover Cu, Co, Ni from copper slag. Beginning in the
tant. Steel slag is usually subjected to metal recovery 1970s, attention was also paid to the treatment of salt
prior to its application outside the iron and steel making slag due to its rapid increase and its serious effect on the
process. By applying mineral processing technologies environment. By mechanical separation and leaching
such as crushing, grinding, classification and magnetic with water, Al metal pieces with 7% yield and salts with
separation, it is possible to produce steel scrap (Fe: 50% yield can be obtained respectively from salt slag.
90%) and iron concentrate (Fe > 55%) from steel slag. The remaining oxides become benign for landfilling or
The amount of stainless steel slag is the largest among further application. In addition, recovery of Nb and Ta
the alloy steel slags and it contains high Cr and a certain from tin slag and Au and Ag from tin slag and other
amount of Ni. Since stainless steel slag can release a slags were also performed.
noticeable amount of Cr as high as 1 ppm and its lea- (4) Incineration slag (or residue) is a relatively new
chate EC50 value exceeds the standard level of 3000 mg/ ever-increasing slag. Since incineration fly ash has high
l, it may cause environmental concerns. It is desirable to heavy metal and dioxin concentrations, it needs special
treat stainless steel slag prior to its application or even treatments, such as vitrification by re-melting, extrac-
landfilling. Recovery of Cr and Ni from stainless steel tion using acid or other solvents and so on. Separation
slag is not only cost-effective, but also very important of metals from incineration bottom ash has been
for the environment. Magnetic separation and gravity applied in industry. Fe, Al, and Cu etc. can be obtained
separation methods were reported for recovery of Cr from bottom ash by mechanical separation incorporat-
and Ni from this slag, but few detailed papers were ing drying, crushing, sieving, magnetic separation and
948 H. Shen, E. Forssberg / Waste Management 23 (2003) 933–949

eddy current separation. After mechanical processing, Gaballah, I., Allain, E., Djona, M., 1997. Extraction of tantalum and
the bottom ash was reported being used in the con- niobium from tin slags by chlorination and carbochlorination.
Metallurgical and Materials Transactions B: Process Metallurgy
struction of roads and dams. But the more secure dis-
and Materials Processing Science 28 (3), 359–369.
posal strategy is to melt the processed bottom ash at Gbor, Philip.K., Mokri, Valentina., Jia, Charles.Q., 2000. Character-
approximately 1200–1400 C (called vitrification) to ization of smelter slags. Journal of Environmental Science and
make the ash stable and non-toxic so as to use it as a Health, Part A: Toxic/Hazardous Substances and Environmental
resource, e.g. construction materials. Recovery of Engineering 35 (2), 147–167.
metals is also performed from vitrification fly ash. For Geiseler, J., 1996. Use of steelworks slag in Europe. Waste Manage-
ment 16 (1-3), 59–63.
example, Pb and Zn concentrates can be obtained by Ghai, V., Noseworthy, W.H., 1998. Resource recovery programs at
the hydrometallurgical method. Lake Erie Steel. Iron and Steel Engineer (USA) 75 (5), 24–29.
Hamamci, C., Ziyadanogullari, B., 1991. Effect of roasting with
ammonium sulfate and sulfuric acid on the extraction of copper and
cobalt from copper converter slag. Separation Science and Tech-
Acknowledgements
nology 26 (8), 1147–1154.
Herreros, O., Quiroz, R., Manzano, E., Bou, C., Vinals, J., 1998.
The authors are grateful to the Minerals and Metals Copper extraction from reverberatory and flash furnace slags by
Recycling Research Center, Luleå University of Tech- chlorine leaching. Hydrometallurgy 49 (1-2), 87–101.
nology, Sweden, for financial support and approval of Hjelmar, O., 1996. Disposal strategies for municipal solid waste
this paper for publication. incineration residues. Journal of Hazardous Materials 47 (1-3), 345–
368.
Huang, X., Wang, F., 2001. An overview of steel slag processing and
utilization. Manganese Ore of China 3 (in Chinese).
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