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Waste Management 23 (2003) 933949

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An overview of recovery of metals from slags


Huiting Shen*, E. Forssberg
Division of Mineral Processing, Lulea University of Technology, S-97187 Lulea, 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 classied 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 discussed the potential eects 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, otation 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
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 classied into three categories,
namely ferrous slag, non-ferrous slag and incineration
slag. Slags usually contain a quantity of valuable metals.
They are actually a secondary resource of metals, rather
than an end-waste and have been applied as a resource
material in many areas. In addition, for some applications, slags have comparable or even better properties
than their competitive materials. The third feature is
that some slags contain a notable amount of harmful or
heavy metals. The release of these metals may cause
environmental problems.
The conventional method for disposal of slags is
dumping. The increasing dump of slags not only occupies plenty of land, but also wastes resources and can
potentially have an impact on the environment due to
water pollution. Therefore, it is desirable to recover
metals from slags and to utilise the slags.

* Corresponding author. Tel.: +46-920-491313; fax: +46-92097364.


E-mail address: huiting.shen@km.luth.se (H. Shen).

Ferrous slag mainly includes iron slag (blast furnace


slag), steel slag, alloy steel slag and ferroalloy slag. Blast
furnace slag (BF slag) and steel slag make up the major
part of ferrous slag. The study and utilisation of BF slag
and steel slag has a long history. For example, as early
as in 1880 they were used as a phosphatic fertiliser
(Geiseler, 1996). Today, BF slag and steel slag have
found a wide application, such as cement production,
road construction, civil engineering work, fertiliser production, landll daily cover, soil reclamation, and so on.
Since BF slag contains little Fe, recovery of Fe from it is
not important. However, steel slag is usually subjected
to metal recovery prior to its application outside the
iron and steel making process. The iron and steel
industry has applied mineral processing technology to
recover steel scrap (Fe: 90%) and iron oxide concentrate
(Fe555%) from steel slag and use them as feed materials for sintering, blast furnace and steel making (Huang
and Wang, 2001). It was reported that the use of the
recycled iron concentrate not only saves metal resource,
but also improves the iron and steel making process due
to Mn, CaO and MgO contents in the recycled material
(Radosavljevic et al., 1996; Svyazhin et al., 1998; Dolgorukov, 1991; Huang et al., 2001). Alloy steel slag and
ferroalloy slag usually contain high amounts of alloy
elements, such as Cr, Ni, Mn, Ti, V, Mo. Recently,
some research work has been done on the treatment of

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H. Shen, E. Forssberg / Waste Management 23 (2003) 933949

the slags, especially on the treatment of stainless steel


slag and charge chrome slag since the former contains
expensive metals Cr and Ni and the latter contains high
amount of Cr (Kortbaoui et al., 1993; Das et al., 1997;
Choudhury et al., 1996). Some commercial plants for
treatment of charge chrome slag and stainless steel slag
have been reported in operation (Lopez et al., 1997;
Salamon, 1995; Khan et al., 2001).
There are many dierent non-ferrous slags generated
from non-ferrous smelters. Perhaps copper slag was
subjected to the most extensive research work with also
a long history of over 100 years (Vircikova and Molnar,
1992). There were numerous reports on recovery of Cu,
Ni, and Co from copper slag (Ziyadanogullari, 2000;
Barnes et al., 1993; Herreros et al., 1998; Basir et al.,
1999). Recently, attention was also paid to the treatment of salt slag since the increasing aluminium recycling has caused a rapid increase of toxic salt slag
(Reynolds and Olper, 1990; Unger and Becker, 1992;
Lopez et al., 1994). Industry now has found methods to
recycle salts and aluminium scrap from salt slag and
turn this toxic slag into useful materials (Reynolds and
Olper, 1990; The Ends Report, 1999; Kirchner, 1991).
In addition, recovery of Nb and Ta from tin slag and
Au and Ag from tin slag and other slags were also
reported (Gaballah et al., 1997; Li et al., 1995).
Incineration slag is a relatively new ever-increasing
slag. Over recent years, several studies have been reported on the treatment, utilisation and metal recovery
from incineration slag, mostly in Germany and Japan
(Kaulbarsch et al., 1997; Pretz and Meier-Kortwig,
2000; Schmelzer et al., 1996; Sakai and Hiraoka, 2000).
Incineration slag processing by mechanical separation
can obtain Fe scrap and non-ferrous metals such as Al,
Cu, Pb, Zn and Ag. This has been applied in industry
although only a few papers were reported recently in
Germany (Kaulbarsch et al., 1997; Pretz and MeierKortwig, 2000).
The generation, characteristics and application of
various slags will now be analysed and summarised,
along with a review of a number of methods for recovery of metals from such slags.

2. Ferrous slag

Hg, Se and Ag) are much lower than the Toxicity


Characteristic Leaching Procedure (TCLP) criterion
concentrations. The results indicate that the elements
are very tightly bound and not released from the matrix
(Proctor et al., 2000). Nowadays almost 100% of BF
slag is utilised in many areas, such as cement production, road construction, civil engineering work, fertiliser
production, landll daily cover, soil reclamation, and so
on (Huang and Wang, 2001). Since BF slag contains
little iron (Fe < 2%), recovery of metals from BF slag is
not important.
2.2. Steel slag
Steel slag is produced from Basic Oxygen Furnace
(BOF steel slag) and Electric Arc Furnace (EAF steel
slag) in the steel making. They are about 1015% by
weight of the steel output (Proctor et al., 2000). Each
year, a great amount of steel slag is produced in the
dierent countries, as shown in Table 1.
2.2.1. Characteristics of steel slag
2.2.1.1. Chemical and mineralogical composition. The
chemical composition of the steel slags from dierent
sources is shown in Table 2 (Motz and Geiesler, 2001;
Okumura, 1993; Bi and Lin, 1999; Fregeau-Wu et al.,
1993). The main components in the steel slags are CaO,
Fe, SiO2, MgO and MnO. Fe in the steel slags is normally in the form of steel (710%), iron oxide and ironbearing minerals. They can be separated from slag by
applying mineral processing technology and recycled as
feed materials for sintering, blast furnace and steel
making. In addition, the high content of CaO, MgO and
MnO in steel slags can be used to substitute for a part of
limestone, dolomite and manganese ore so as to reduce
iron and steel making cost. Some steel slags contain
higher amount of P2O5 and S than iron concentrate.
This may aect the direct recycling of the steel slags to
the iron and steel making process.
The main mineral phases of steel slag are metallic iron,
dicalciumsilicate (2CaO.SiO2), dicalciumferrite (2CaO.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
example, slow cooling of a typical BOF slag can produce
larger phase grains than fast cooling (Fregeau-Wu et al.,

2.1. Iron slag


Iron slag is generated from Blast Furnace (BF slag) in
the iron production, with 220370 kg slag per ton of
iron being produced (Proctor et al., 2000). The amount
of BF slag is the largest among the ferrous slags. For
example, In USA and Japan, 13 and 24.3 million tons of
BF slag were produced each year (Proctor et al., 2000;
Okumura, 1993). Leaching study shows that the concentrations of elements (including As, Ba, Cd, Cr, Pb,

Table 1
Production of steel slag in the dierent countries
Country

Steel slag (BOF+EAF)


(Million ton)

Reference

Europe
USA
China
Japan

12
8
14.07
12.6

Motz and Geiseler (2001)


Proctor et al. (2000)
Huang and Wang (2001)
Okumura (1993)

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H. Shen, E. Forssberg / Waste Management 23 (2003) 933949


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

CaO

MnO

MgO

SiO2

P2O5

Al2O3

1420
1520
1828
2029

4555
4250
3040
2535

<5
<5
<6
<6

<3
58
48
815

1218
1215
1217
1015

<2
<2
<1.5
<1.5

<3
<3
47
47

NR
NR
NR
NR

BOF slag (converter)


EAF slag (electric furnace oxidation)

17.5
15.2

44.3
38.0

5.3
6.0

6.4
6.0

13.8
19.0

NR
NR

1.5
7.0

0.07
0.38

China

BOF slag

1727

3448

1.56

2.510

915

0.9

0.92.8

0.2

USA

BOF slag

1530

4050

510

510

1015

13

NR

Country

Slag

Europe

BOF slag
BOF slag
EAF slag
EAF slag

Japan

low MgO content


high MgO content
low MgO content
high MgO content

NR=no report.

1993). At higher basicities (CaO/SiO2+P2O5 > 2.5),


tricalciumsilicate and lime (CaO) become dominant in
steel slag (Huang and Wang, 2001). Other minerals
reported in steel slag include periclase, manganosite, Fe
and Mn monticellite, Mn-cordierite, glass, and (Fe, Mn,
Mg) oxide solid solution (Radosavljevic et al., 1996).
2.2.1.2. Leaching behaviour of steel slag. The release of
metals or harmful elements from slags will cause environmental problems such as water pollution and soil
pollution, and a toxicological risk to humans through
the inhalation of small slag particles ( < 10 mm). Proctor
et al. (2000) recently reported a detailed study on the
leaching behaviour of iron and steel slags in the USA, as
shown in Table 3. From the results, it can be seen that
none of the metals (elements) in the leachates exceeds
the TCLP criterion concentrations in the TCLP test.
Therefore, iron and steel slags should not be considered
a hazardous waste. Similar results and conclusions were
also reported earlier by Geiseler (1996).
2.2.1.3. Technical properties of steel slag. The application of slags is closely related with their technical properties. These are also the important data relevant to slag
processing, e.g. for crushing or grinding. Some properties

of steel slags were investigated and compared with those


of natural aggregates by Geiseler, as shown in Table 4
(Geiseler, 1996). From Table 4, it can be seen that (a)
the density of steel slags is higher than the natural
aggregates (steel slags contain a high amount of iron),
(b) steel slags are a hard material (the compressive
strength is close to granite), (c) the resistance of steel
slags to impact is approximately the same as the natural
aggregates (indicating they are dicult to crush) and
nally (d) the Los Angeles test values are also high
(indicating they are dicult to grind).
Moreover, since steel slags contain some reactive
minerals such as 2CaO.SiO2, 3CaO.SiO2 and free CaO
and MgO, they are a water-hardenable material (Steel
Today and Tomorrow (Japan), 1993; Huang and Wang,
2001). When steel slags comprise a certain amount of
free CaO or MgO, they are not stable in volume due to
the hydration of free CaO or MgO (Geiseler, 1996; Ghai
and Noseworthy, 1998; Huang and Wang, 2001).
2.2.2. Application of steel slag
Steel slag has been applied in many areas, as summarised in Fig. 1 (Okumura, 1993; Huang and Wang,
2001; Geiseler, 1996; Svyazhin et al., 1998). Basically,
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)

Arsenic
Barium
Cadmium
Chromium (VI)
Chromium (total)
Lead
Mercury
Selenium
Silver

TCLP screening criterion


concentrationa (mg/l)
5
100
1
5
5
5
0.2
1
5

TCLP leachate concentration

Exceed criterion?

BF

BOF

EAF

BF

BOF

EAF

0.0048
1.2
0.0054
0.026
0.22
ND
ND
ND
ND

0.0054
0.88
0.01
ND
0.04
0.015
0.0005
ND
0.029

0.011
1.67
0.037
0.018
1.0
0.063
0.00089
0.0073
0.027

No
No
No
No
No
No
No
No
No

No
No
No
No
No
No
No
No
No

No
No
No
No
No
No
No
No
No

ND=not detected.
a
From Method 1311 Toxicity Characteristic Leaching Procedure.

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H. Shen, E. Forssberg / Waste Management 23 (2003) 933949

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

Unit

BOF slag

EAF slag

Basalt

Granite

Bulk density
Resistance to impact determined on crushed aggregates (812 mm)
Absorption of water
Freeze/thaw resistance (particle size < 5 mm)
Los Angeles test (test aggregates: 812 mm)
Polished stone value (PSV)
Compressive strength

g/cm3
wt.%
wt.%
wt.%
wt.%

3.13.7
1026
0.21.0
< 1.0
918
5457
> 100

3.23.8
1026
0.21.0
<1.0
815
5863
>100

2.83.1
920
<0.5
<1.0

4555
>250

2.62.8
1227
0.31.2
0.82.0
1520
4555
>120

N/mm2

Fig. 1. Utilization of steel slag.

direct application of steel slag in the iron and steel


making process; the other includes recovery of metals
from steel slag and then the application of the remaining steel slag outside the iron and steel making process.
As shown in Table 2, steel slag contains about 3050%
CaO and 310% MgO. It can be directly used as a ux in
sintering, blast furnace or steel making process for substitution of a part of limestone and dolomite. In this
process, Fe in the steel slag is recovered too. In addition,
the use of steel slag in the iron and steel making process
can also save manganese ore and improve the process
because there is some MnO in the steel slag. However,
since some steel slags contain a notable amount of P and
S, which are harmful to iron and steel making, and
approximately 1018% SiO2, the amount of direct use of
steel slag in the iron and steel making process is limited.
The other part of steel slag (5090% of the total steel
slag) is usually subjected to metal recovery and then
applied outside the iron and steel making process.
About 85100% of annual production of steel slag has
been applied now in many countries. Table 5 is an
example of the utilization of converter slag in Japan
(Okumura, 1993).

2.2.3. Recovery of metal from steel slag


As mentioned above, steel slag is usually subjected to
metal recovery prior to its application outside iron and
steel making process. The methods for slag processing
are dierent, depending on the cooling method, chemical and mineralogical composition of steel slag, and its
application. In general, steel slag processing includes
crushing or grinding, screening and magnetic separation, and sometimes removal of P (Huang and Wang,
2001; Radosavljevic et al., 1996; Fregeau-Wu et al.,
1993).
2.2.3.1. Size reduction of steel slag. In order to liberate
metallic iron and iron-bearing minerals from steel slag
and process steel slag for application, size reduction is
necessary. This is achieved in two ways. One is multicrushing with crushers. A jaw crusher is generally used
for the primary crushing, while a cone crusher, hammer
crusher or impact crusher is used for the secondary
crushing. It was reported that a roll crusher is not suitable for this operation (Huang and Wang, 2001).
The other way for size reduction of steel slag is onestage dry autogenous grinding. One advantage is that

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H. Shen, E. Forssberg / Waste Management 23 (2003) 933949


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

Ratio of utilization
Production
(103 t/year) (%)

Utilization
Unit

Metal recovery Road

103 t/year 195


%
1.92

Cement Earth works Fertilizer Others

814
692
7.99
6.80

3316
32.57

124
1.22

one autogenous grinding machine can replace several


crushers in multi-crushing so that its operation is simple. Moreover, the metallic iron product discharged
from the grinding machine contains Fe as high as 80%.
By autogenous grinding, magnetic separation and
screening, 8% metallic iron, 47% iron concentrate and
85% slag product can be obtained (Liu, 1991).
2.2.3.2. Classification and magnetic separation. The
magnetic separation method is used for separating
metallic iron and iron minerals from steel slag. Commonly-used magnetic machines are cross-belt magnetic
separator, drum magnetic separator and magneticpulley separator. To improve magnetic separation eciency, the classication of steel slag fed to magnetic
separation is carried out. A single or double-deck
vibrating screen is used for this process. Screens (including bar screen) are also used in the crushing circuit or in
classication of nal slag product for dierent applications, as shown in Fig. 2 (Huang and Wang, 2001).
2.2.3.3. Removal of P from steel slag. Since some steel
slags contain a notable amount of P (13%), it is
necessary to remove the P to recycle more slag to the
iron and steel making process. The study results reported by Fregeau-Wu et al. (1993) show that P in steel slag
occurs predominantly in dicalcium silicate and to a lesser
extent in dicalcium ferrite in solid solution. High gradient
magnetic separation was used to separate the P-bearing
dicalcium silicate from the iron- and manganese-bearing

Using in own works Total

1080
3960
10.61
38.89

10,181 9965
100

102.2

minerals. In a separation test of an as-received slag,


50% of the P reported to the tailings. It was also found
that slow cooling of steel slag promotes mineral grain
growth and the formation of calcium phosphate which
occurs as ne-grained crystals associated with the dicalcium silicate matrix. Hence slow cooling will improve
the liberation of minerals and the separation process.
About 70% of the P was removed from slow-cooled slag
by high gradient magnetic separation.
2.3. Alloy steel slag
Various alloy steel slags are generated in the alloy
steel making processes. Compared with BF slag and
steel slag, the amount of alloy steel slags is small but
they usually contain high amounts of alloy elements,
such as Cr, Ni, Mn, V, Ti, Mo. Since the amount of
stainless steel slag is the largest among the alloy steel
slags and since it contains high content of Cr and a
certain amount of Ni, it is necessary to treat stainless
steel slag prior to its application or landlling. Recovery
of Cr and Ni from stainlees steel slag is not only signicant in economy, but also very important for the
environment.
2.3.1. Chemical and mineralogical composition of
stainless steel slag
In the stainless steel production, EAF stainless steel
slag and Argon Oxygen Decarburization (AOD) stainless steel slag are generated. Table 6 shows the chemical

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

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H. Shen, E. Forssberg / Waste Management 23 (2003) 933949

Table 6
Chemical composition of stainless steel slags

Table 8
Chemical analysis of leachates, ppm and EC50 values (mg/l)

Component

Element

CrTotal Pb

Cd

Fe

Mn Ni

Cu

EC50

pH

AOD

1.0
1.0
1.0
<5

<0.1
<0.1
<0.1
<1

<0.5
<0.5
<0.5

0.5
0.5
0.5

< 0.5
< 0.5
< 0.5

>3000
>3000
>3000
<3000

11.0
9.5
10.0

AOD slag

CaO
SiO2
Al2O3
MgO
MnO
FeTotal
Na2O
K2O
CrTotal
Cu
Ti
Zn
Pb
Ni
Cd
Free CaO
Loss on ignition
Basicity (CaO/SiO2)

47.60
31.24
1.66
3.65
1.60
1.75
0.08
0.05
3.47
0.05
0.13
0.02
0.05
0.25
<0.01
3.21

1.52

45.50
26.32
9.69
7.30
2.06
3.50
0.07
0.05
4.28
0.05
0.68
0.02
0.05
0.22
<0.01
0.51

1.75

45.50
27.61
1.65
7.30
1.41
7.40
0.03
0.05
2.48
0.12
0.20
0.03
0.04
0.45
<0.01
0.91
7.14
1.65

composition of some AOD slags (Lopez et al., 1997).


Compared with steel slag (Table 2), the contents of
CaO, Al2O3, MgO and MnO in AOD slag are close to
those in steel slag, but SiO2 is much higher than in steel
slag. Therefore, the basicity of AOD slag is lower than
steel slag. Moreover, AOD slag contains much less iron
than steel slag. Hence recovery of iron from AOD slag
is not important. Perhaps the most important characteristic of AOD slag is that it contains a high amount
of Cr (2.54.3%) and some Ni (0.20.45%).
The mineralogical composition of the AOD slags is
shown in Table 7. Similar to steel slags, AOD slags also
consist mainly of dicalcium and tricalcium silicates,

4
5
6
Standard

< 0.5
< 0.5
< 0.5
<5

<0.5
<0.5
<0.5

EC50 is the biotoxicity of a solution determined by luminescence


bioassay with photobacterium phosphoreum in a Microtox toxicity
analyzer.

calcium-aluminium silicates and free lime and periclase


except that they contain chrome-nickel-magnesium
oxide solution in the form of chromites in which Cr and
Ni exist (Lopez et al., 1997).
2.3.2. Leaching behavior of AOD slag
The leaching results in Table 8 show that AOD slag
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 (dened in Table 8)
exceeds the standard level of 3000 mg/l (Lopez et al.,
1997). Therefore AOD slag might be a hazardous slag.
In the AOD processing plants, dust control must be
strict for the dry treatment, and further disposal of
plant waste water from the wet treatment needs to be
taken into consideration.
2.3.3. Recovery of metals from stainless steel slag
It is reported that magnetic separation or gravity
separation methods have be used for recovery of Ni and
Cr from stainless steel slag in some commercial processes (Lopez et al., 1997). But few detailed papers are
published. It seems that more eorts need to be made

Table 7
Mineralogical composition of AOD slags
AOD slag

Element
Ca

Si

Al

Mg

Mn

Fe

Cr and Ni

Melilite
Merwinite
C2S
C2S.SiO2
Fluorite
Melilite
Merwinite
Ti-CaOxide
Melilite
Merwinite
C2S
C2S.SiO2
Calcite
Fluorite

Silicate

Melilite

Silicate
periclase

Chromites

Chromites

Chromites

Silicate

Melilite

Silicate
periclase

Chromites

Chromites

Chromites

Silicate

Melilite

Silicate
periclase
MgO.Cr2O3

Chromites

Chromites
a Fe

Chromites

C2S, dicalcium silicate; C3S, tricalcium silicate.

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H. Shen, E. Forssberg / Waste Management 23 (2003) 933949


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

812

Stainless steel slag

37

2632

4548

37

29

34

for treating stainless steel slag and recovering Ni and Cr


from it.
2.4. Ferroalloy slag
Ferroalloy slag includes FeMn slag, SiMn slag and
CrFe (charge chrome) slag etc. Since charge chrome slag
contains high content of Cr, more attention has been
focused on the treatment of it and recovery of Cr from
it. It is estimated that an almost equal amount of slag
and metals are produced in a charge chrome plant. A
number of papers have been published describing the
characteristics of charge chrome slag and the methods for
recovery of Cr from the slag. Recently, some commercial
plants for recovery of Cr from charge chrome slag in
India and South Africa were also reported (Khan et al.,
2001; Salamon, 1995; Mashanyare and Guest, 1997).
2.4.1. Chemical and mineralogical composition of charge
chrome slag
The main components of charge chrome slag are
MgO, SiO2, Al2O3, Cr2O3, CaO and FeO. A comparison
of chemical composition of charge chrome slag with
stainless steel slag is shown in Table 9. The contents of
Fe and SiO2 in the charge chrome slag are similar to
those in the stainless steel slag. CaO is much lower but
MgO and Al2O3 are much higher in the former than in
the latter. Charge chrome slag usually contains 812%
Cr, which is higher than in stainless steel slag. Therefore, treatment of charge chrome slag is also necessary.
The mineralogical study results by Das et al. (1997)
show that the major phases in charge chrome slag are
spinel and non-crystalline glassy CaMgAl silicate. The
minor phases include olivine, chromite and metallic phases. The chromite comes from the unreacted chromite ore
grain. X-ray diraction (XRD) data and scanning electron microscope (SEM) studies indicate that metallic
phases are mainly (CrFe)7C3. Cr appears mainly in chromite and metallic phases. A small amount of Cr is also
found in spinel (Cr2O3: 25%) and olive (Cr2O3 < 1%).
2.4.2. Recovery of Cr from charge chrome slag
The methods reported for recovery of Cr from charge
chrome slag include magnetic separation and gravity
separation.

Choudhury et al. (1996)


Das et al. (1997)
Khan et al. (2001)
Lopez et al. (1997)

Das et al. (1997) used magnetic separation method to


treat a charge chrome slag. The pilot test shows that a
Cr concentrate with grade of 57.1% Cr2O3 and yield of
1.5% can be obtained from a charge chrome slag (particle size: 8 mm) containing 9.3% Cr2O3. A two-step
magnetic separation is used; dry belt magnetic machines
(belt width: 381 mm) at 1000 Gauss magnetic intensity
are used for the rst step and 800 Gauss for the cleaning
step. However, up to date no commercial processes
using magnetic separation method to treat charge
chrome slag have been reported.
Gravity separation method seems relatively more
eective for the treatment of charge chrome slag
according to some reports. The sink-oat test results
presented by Choudhury et al. (1996) show that it is
possible to produce a concentrate of 55% Cr with a
yield of 3% at the crushing particle size of 5 mm from
a charge chrome slag containing 11.5% Cr. Khan et al
(2001) also described the gravity separation process for
recovery of Cr from a charge chrome slag of 11.53% Cr.
The slag was subjected to two-stage crushing to reduce
the size to 10 mm and then screened into 10+1 mm
and 1 mm fractions. The coarse fraction was subjected
to jigging and the ne fraction to tabling. The jigging
produced a product analyzing 59.2% Cr with 6.7%
yield, while the tabling produced a low grade of concentrate containing 29.2% Cr.
Gravity separation methods for recovering Cr from
charge chrome slag have been applied in industry. In
South Africa, a charge chrome slag commercial plant
with a capacity to recover 50 kt/a of ferrochrome was
reported in operation in 1995. Jigging was adopted in
the plant for the coarse fraction (25+1 mm) and
spiral for the ne fraction (1 mm) (Salamon, 1995). In
India, a charge chrome slag and mixed metal commercial plant designed by Svedala was also reported in
operation in 2000 (Khan et al., 2001).
2.4.3. Leaching behavior and treatment problems of
charge chrome slag
Systematic studies on leaching behavior of charge
chrome slag have not been reported, but the analysis of
the water sample from a jigging processing plant of
charge chrome slag shows that it contains Cr+6 as high
as 1.6 mg/l, which is higher than the level < 0.1 mg/l

940

H. Shen, E. Forssberg / Waste Management 23 (2003) 933949

stipulated by the World Health Organization for discharge into lakes and rivers (Coetzer et al., 1997). In
view of this fact, charge chrome slag may be also a
hazardous slag and care must be taken for the treatment
of this slag. Further disposal of the plant water from
wet treatment is necessary and dust control must be
strict in the dry processes.

3. Non-ferrous slag
There are a variety of non-ferrous slags produced
from non-ferrous smelters. Extensive studies on metal
recovery from non-ferrous slags have been carried out
for the past decades. Most of the studies were on metal
recovery from copper slag. Recently, attention was also
paid to the treatment of salt slag due to its rapid
increase and its serious eect on the environment. There
were also additional reports on recovery of Nb and Ta
from tin slag, Au and Ag from tin slag or other slags
and so on. Unlike iron and steel slags, the application of
non-ferrous slags may cause environmental concerns
since they usually contain a notable amount of heavy
metals or even toxic elements with a relatively high
solubility (Manz and Castro, 1997; Atzeni et al., 1996).
The reports on the application of non-ferrous slags are
relatively few.
3.1. Copper slag
3.1.1. Chemical and mineralogical composition of copper
slag
The chemical composition of copper slags from different origins is shown in Table 10. In general, the main

components in the copper slags are Fe and SiO2 with


amount of 2550% for each. Almost all copper slags
contain a considerable amount of Cu (0.53.7%) close
to or even higher than copper ores. Depending on the
origins, some slags contain Co and/or Ni at levels worthy of recovery and utilization. Toxic elements (As) and
heavy metals (Pb) exist in some copper slags (see slag 3
and slag 6). Slag 6 is a brass smelting slag quite dierent
from the ordinary reverbratory and ash slags. It contains high Cu and Zn and some Pb.
The mineralogical composition and phase grains
within copper slags from dierent origins are quite different, depending on many factors such as the type of
ores processed, the type of furnaces and the cooling
methods (Gbor et al., 2000). Slow cooling may result in
a signicant crystallization of slag components, forming
a large number of dierent mineral phases. The lower
the cooling rate, the larger the mineral phases grow
(Rao and Nayak, 1992). Fast cooling may produce an
amorphous slag and hence the slag is more homogeneous in metal distribution. When copper slag is
crystalline, the major phases are usually fayalite along
with other silicates. In most cases Ni and Co are in the
form of oxides (Gbor et al., 2000). Some studies show
that Co distribution in the slags is very homogeneous.
However, the forms of Cu minerals are dierent in different copper slags. They may be in the form of oxides
or suldes or a mixture of them. Copper suldes are
also dierent in dierent copper slags. For instance, slag
1 in Table 10 was reported containing covellite (CuS),
slag 3 containing chalcocite (Cu2S) and metallic copper,
Slag 4 containing chalcocite, bornite(Cu5FeS4), metallic
copper, stromeyerite and complex sulphides, and slag 5
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
Co
Ni
Ag (ppm)
Pb
Zn
Fe
SiO2
Al2O3
CaO
MgO
Mn
Ti
S
As

2.60
0.36
0.045
NR
NR
0.425
52.0
NR
NR
NR
NR
NR
NR
4.90
NR

0.58
0.21
0.57
NR
NR
NR
38.6
Si: 17.40
Al: 2.51
Ca: 1.11
Mg: 1.65
0.03
0.15
0.93
NR

3.70
0.25
NR
2
0.18
0.44
49.99
22.45
1.14
NR
NR
NR
NR
1.56
0.05

1.22
NR
NR
NR
NR
NR
32.24
NR
NR
NR
NR
NR
NR
NR
NR

2.753.30
0.50.7
0.91.2
NR
NR
NR
4548
2426
NR
NR
NR
NR
NR
NR
NR

20.7
NR
NR
NR
1.33
11.35
NR
NR
NR
NR
NR
NR
NR
NR
NR

0.63.2
NR
NR
NR
NR
NR
32.737.3
32.537.3
2.44.0
1.87.5
1.64.0
NR
NR
0.51.0
NR

Slag 1: Converter slag from Ergani Mining Co., Turkey (Altundogan and Tumen, 1997). Slag 2: Slowcooled slag from INCOs ash 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 Remet 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 EIMaady 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) 933949

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 classied into
three categories, namely otation, leaching and roasting.
Barnes et al. (1993) described an industrial otation
process of the copper slag at Mount Isa Mines Limited.
The slag is ground to 80%74 mm prior to otation.
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 otation tail. A
similar result was reported by Rao and Nayak (1992). In
the otation experiment of a converter slag (3.7% Cu,
cooled in a refractory lined pit) with potassium amyl
xanthate as collector, pine oil as frother at pH 89, a
concentrate containing 44% Cu was obtained with 96
recovery. Co and Ni were also reported in tailings.
In principle, copper slag otation is the same as sulde ore otation. This means only metallic Cu and sulde minerals can be oated eectively. 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 otation method will not be eective for recovery of
Co, Ni and oxide Cu. Therefore, the application of otation in copper slag processing could be limited.
Leaching is another method for extraction of metals
from copper slags. The leachants applied in slag leaching include sulfuric acid, hydrochloric acid, ferric chloride, ammonia, cyanide and so on (Basir et al., 1999;
Anand et al., 1980). Cyanide was used in the early time,
but was replaced by other leachants due to environmental problems. To increase leaching eciency, some
measures, such as addition of H2O2, pressure leaching
or leaching in Cl2/Cl system, were taken. For example,
in the leaching of a brass smelting slag containing 6.3%
Cu (free metal), 14.4% Cu (oxide form), 11.35% Zn
(oxide form) and 1.33% Pb (oxide form) with hydrochloric acid or ammonia, addition of H2O2 greatly
increased the extent of metal extraction, especially in the
hydrochloric acid leaching, as shown in Figs. 3 and 4
(Basir et al., 1999). It was reported that by pressure
leaching with dilute sulphuric acid about 90% Cu and
more than 95% each of Ni and Co could be extracted
with only 0.8% extraction of Fe from a copper converter slag containing 4.03% Cu, 1.98%Ni and 0.48%
Co (Anand et al., 1983). Cl2/Cl (from reaction of
NaOCl and HCl) leaching method was adopted for
extraction of Cu from the reverberatory and ash furnace slags containing metallic Cu and Cu sulde minerals and complex suldes with very small size, mainly
510 mm. Extraction of 75 to 80% Cu and 5% Fe were
obtained at room temperature (Herreros et al., 1998).
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

941

Fig. 3. Eect of H2O2 addition on extraction of Cu, Zn and Pb from


brass smelting slag in HCl leaching.

Fig. 4. Eect of H2O2 addition on extraction of Cu, Zn and Pb from


brass smelting slag in NH4OH leaching.

metals in various forms in slag are reduced into free


metals. Then otation or leaching is used for separation
of the metals from the slag (Vircikova and Molnar, 1992).
A more simple and eective method is called sulfating
roasting, in which Cu, Co and Ni in various forms are
converted into soluble sulfates through a series of chemical reactions at 200600 C by addition of sulde or sulfate agents (Tumen and Bailey, 1990; Hamamci and
Ziyadanogullar, 1991; Ziyadanogullarii, 1992, 2000;
Altundogan and Tumen, 1997). Then the soluble sulfates
are dissolved in water and separated from the slag. The
sulde and sulfate agents used in the roasting include
H2S, H2SO4, (NH4)2SO4, Fe2(SO4)3xH2O and pyrite. The
chemical reactions in the sulfurization process with H2S
summarized by Ziyadanogullari (1992) are shown below:
Fe3 X4 H2 S 6H *
) 3Fe2 S 4H2 X

Cu2 O H2 S *
) Cu2 S H2 O

2Cu H2 S 1=2O2 *
) Cu2 S H2 O

Co3 X4 4 H2 S *
) 3 CoS S 4 H2 X

where X=O2 or SiO2


3 .

942

H. Shen, E. Forssberg / Waste Management 23 (2003) 933949

The suldes Cu2S and CoS are then converted into


soluble CuSO4 and CoSO4 during roasting at
600700 C. Ziyadanogullari (2000) used a sulfating
roasting method to treat a converter slag containing
2.4% Cu, 0.38% Co, 50.3% Fe and 2.92% S. By sulfurization in a closed system at 130  C for 1 h with (6.1
g H2S+25 g H2O)/100 g slag, and then by roasting at
600 C for 6 h, the amounts of Cu and Co dissolved in
water were 99.2 and 98.8%.
In fact, the chemical reactions in the roasting process
with the addition of Fe2(SO4)3x.H2O (or H2SO4 and
(NH4)2SO4) are dierent from the above. There are not
sulfurization reactions in this process. The function of
Fe2(SO4)3xH2O is to generate SO3 which can react with
metal oxides to produce sulfates when it decomposes
above 480 C. A series of chemical reactions described
by Altundogan and Tumen (1997) are shown as follows:
Fe2 SO4 3 *
) Fe2 O3 3 SO3 or SO2 1=2 O2

M 1=2 O2 *
) MO

MS 3=2 O2 *
) MO SO2

MO SO3 *
) MSO4

2MO SO3 *
) MOMSO4

MO Fe2 O3 *
) MOFe2 O3

10

where M=divalent metals.


It was reported by Hamamci and Ziyadanogullari
(1991) that H2SO4 is better than (NH4)2SO4 as a sulphating agent for roasting of a converter slag containing
2.56% Cu, 0.22% Co and 49.0% Fe. Under the condition of roasting at 200 oC for 60 min with 1.5 times the
stoichiometric amount of H2SO4, Cu and Co recoveries
were 82 and 96% respectively.

waste (Lopez et al., 1994). Treatment of salt slag is


important not only for the environment, but also for
reduction of landlling cost for the secondary aluminum
industry (The Ends Report, 1999; Reynolds and Olper,
1990).
Study on the utilization of salt slag began in the
1970s. It was reported that in 1977 a company called
Engitec designed and installed the rst generation salt
recovery system at Carisio, Italy (Reynolds and Olper,
1990). In 1986, a more versatile commercial plant developed by B.U.S (Berzelius Umwelt Services AG) in Germany for recovery of aluminum scrap and salts and
treatment of the noxious gases from salt slag was reported in operation (Beckmann, 1991; Unger and Beckmann, 1992). Nowadays, most commercial plants use the
methods similar to the B.U.S process (Metal Bulletin,
1997; Kirchner, 1991; Reynolds and Olper, 1990)
3.2.1. Chemical and mineralogical composition of salt
slag
Tables 11 and 12 show the chemical and mineralogical
composition of a salt slag respectively (Lopez et al.,
1994). From the results, it can be seen rstly that the
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
small amount of AlN, Al4C3 and Al2S3 etc. This means
that the maximum yield of recovering aluminum scrap
from the salt slag by mechanical separation is only
7.25%. Secondly, the results show that approximately
50% of salt slag is made up of water-soluble minerals.
They are halite (NaCl) and sylvite (KCl) and a small
content of aluminum nitride (AlN), aluminum carbide
Table 11
Chemical analysis of salt slag
Element Al
wt.%

Na

Si

Mg

Ca

Fe

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
industry. During the smelting process of recycled aluminum scraps in reverberatory or rotary furnace, uxes
consisting of NaCl and KCl are added on the molten
bath to prevent metal oxidation and remove impurities
from the charge, and thus salt slag is formed. Approximately 0.5 tons of salt slag arises when producing one
ton of secondary aluminum (Kirchner, 1991; Lopez et
al., 1994). Over recent years, the increasing aluminum
recycling has caused a rapid increase of salt slag.
Salt slag contains a great amount of water-soluble
compounds. When salt slag contacts rainfall or
groundwater, it will release chlorides into the water and
give o noxious gases including H2, NH3, CH4, H2S and
PH3. It has been classied as a toxic and hazardous

Table 12
Mineralogical composition of salt slag
Mineral

wt.%

Al metal
AlN
Al4C3
Al2S3
MgO.Al2O3
Al2O3
bCaO.SiO2
SiO2
Na2O.SiO2
K2O.SiO2
NaCl
KCl
FeSi

7.25
2.10
2.40
0.20
16.59
7.68
2.68
1.85
4.30
0.48
41.92
4.66
0.75

H. Shen, E. Forssberg / Waste Management 23 (2003) 933949

(Al4C3) and aluminum sulphide (Al2S3) etc. Thirdly, the


remaining part of the salt slag is shown to be mainly
non-soluble Al, Mg, Ca and Si oxides, including corundum (Al2O3), spinel (MgO.Al2O3), quartz (SiO2) and
calcium silicate (b-CaO.SiO2).
3.2.2. Leaching behavior of salt slag
Since salt slag contains a large amount of NaCl and
KCl, it will release the chlorides into water when it
contacts waterfall or groundwater. In addition, metallic
aluminum and some aluminum compounds in the salt
slag can react with water and give o noxious gases, as
shown below (Reynolds and Olper, 1990):

Al 3 H2 O AlOH3 3=2 H2 "

11

AlN 3 H2 O AlOH3 NH3 "

12

Al4 C3 12 H2 O 4 AlOH3 3 CH4 "

13

AlP 3 H2 O AlOH3 PH3 "

14

Al2 S3 6 H2 O 2 AlOH3 H2 S "

15

Therefore, direct landlling of salt slag may cause


serious environmental problems. Accordingly, the cost
of landlling salt slag is high, for example, 3035 per
ton in the UK (Metal Bulletin, 1997). Thus, treatment
and utilization of salt slag is important not only for
environmental protection and resource recovery, but
also for reduction of landlling cost for the secondary
aluminum industry.
3.2.3. Treatment and utilization of salt slag
The treatment and utilization of salt slag consists of
three parts, i.e. recovery of Al metal, recovery of salts
and further processing of the remaining oxides. As
mentioned above, the method used in most commercial
plants now is similar to the B.U.S process. It is comprised of ve major steps, namely (a) metal separation

943

(b) leaching (c) solid liquid separation (d) gas treatment


and (e) evaporation and crystallization (Beckmann,
1991; Unger and Beckmann, 1992).
3.2.3.1. Metal separation. The rst step is a dry separation of metallic Al from oxides and salts. Al metal is
ductile, but oxide and salt aggregates are brittle. Utilizing this dierence, multi-stage crushing and screening
are used to separate the Al metal from the oxides and
salts, as shown in Fig. 5. Through this separation, clean
Al metal pieces with approximately 7% yield can be
obtained from salt slag.
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
passed through a bag collector to capture any dust
before venting.
3.2.3.2. Leaching. The oxide and salt powder from the
rst step is then subjected to leaching with water. The
oxides are not soluble while the salts will be dissolved
into water. This makes it possible to separate the salts
from the oxides.
3.2.3.3. Solid liquid separation. After dissolution of the
salts in the oxide and salt powder, the solidliquid mixture is pumped to a thickener. The underow of the
thickener is ltered and washed with recycled water.
Then the clean oxides are available for sale or further
processing. The overow of the thickener and the ltered water are salt-rich solution (brine) which is sent to
evaporation and crystallization step.
3.2.3.4. Gas treatment. In the leaching, thickening and
ltering processes, noxious gases are generated. They
must be captured, diluted to eliminate explosion risk
and then treated to remove the noxious constituents.
In the B.U.S process, the gases are passed through a
scrubber to remove the particulates. Then the clean
gases are sent through a chemical column with sulfuric
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) 933949

Table 13
Variation in contents of Al component with calcinations temperature
Temperature ( C)

Component (wt.%)

Al metal
gAl2O3
aAl2O3
Al2O3.MgO
Al2O3Totala
Al4C3
Al2S3
AlN
a

500

700

1000

1200

1300

1500

3.70
20.37
20.92
25.74
67.30
1.40
0.19
0.36

2.70
24.66
27.69
25.74
70.40
0.60
0.20
0.30

1.50
9.25
46.50
30.42
76.20
0.40
0.06
0.10

0.95
5.45
47.48
31.59
77.30
0.18
0
0.07

0.90
0.38
55.79
30.42
77.30
0.16
0
0.05

0.90
0.38
53.60
31.59
76.60
0.064
0
0.04

Al2O3Total=gAl2O3+aAl2O3+alumina in Al2O3.MgO.

passed through a multi stage absorber to remove other


noxious gases. In some other plants, the noxious gases
are burnt in an afterburner.

foundry and steel mixes, refractory, mineral wool,


abrasives and ceramic bres.
3.3. Other non-ferrous slags

3.2.3.5. Evaporation and crystallization. The clear salt


brine from the thickener and lter is boiled in a
multi-eect evaporator in which water is boiled away
and NaCl and KCl crystals grow from the resulting
saturated solution. Finally, a salt product with a
yield of about 50% can be produced from the salt
slag.
In general, most salt slag processing plants did not
report the further treatment of the remaining oxides.
Only some laboratory results were reported. For example, Lopez et al. (1994) used calcination to treat the
leaching residue of salt slag. By calcination at high
temperature, most Al and its compounds in the residue
are converted into a-Al2O3 and Al2O3.MgO, as shown
in Table 13. It was estimated that the calcination product can be applied in fused grain, cement and glass,

Recoveries of metals from other non-ferrous slags


were also reported. One example is the recovery of Au
and Ag from a pyrite slag or tin slag. The methods
reported for Au and Ag recovery from the slags are
similar to those for treating copper slags above, including otation or roasting (Li et al., 1995).
Another example is the recovery of Nb and Ta from a
tin-slag reported by Gaballah et al. (1997), as summarized in Fig. 6. Before chlorination, Fe, Ca, Mn, and Al
etc. are removed from the tin slag by leaching (acid or
successive acid and basic). Then, the Nb and Ta concentrate is subjected to chlorination at 5001000  C for
24 h with (Cl2+N2) or (Cl2+CO+N2). Nb and Ta
oxides in the concentrate are converted into volatile Nb
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
LGCa
HGCb

5.2
6.3
28.0

7.5
13.7
31.1

41.9
43.3
10.0

11.6
9.8
0.6

3.3
2.5
0.2

11.2
5.2
0.6

0.7
0.9
0.2

3.7
2.3
0.0

1.4
0.8
0.4

1.3
1.2
1.4

20

a
b

Lowgrade concentrate.
Highgrade concentrate.

945

H. Shen, E. Forssberg / Waste Management 23 (2003) 933949


Table 15
Results of chlorination of the Nb and Ta concentrates
Concentrates

Chlorination with Cl2+N2

Chlorination with Cl2+CO+N2

Nb and Ta
recovery (%)

Purity of Nb and
Ta product

Conditions

Nb and Ta
recovery (%)

Purity of Nb and
Ta product

Conditions

LGC

Nb: >95 Ta: >95

1000 C, 24 h

Nb: >95 Ta: >95

Nb: 84 Ta: 65

1000 C, 24 h

Nb: 100 Ta: 100

Not high, contaminated by


chlorides of Fe, Mn, etc.
Pure

1000 C, 24 h

HGC

Not high, contaminated by


chlorides of Fe, Mn, etc.
Pure

residue. The chemical composition is shown in Table 14


and the results of chlorination are summarized in
Table 15. It can be seen that the optimum combination
is the chlorination of high grade concentrate (HGC)
with (Cl2+CO+N2) at temperature 4500 C for a
reaction time of 24 h.

4. Incineration slag
With an increase in municipal solid waste (MSW) and
landll cost, more and more MSW is treated by incineration. For example, in Switzerland, Japan, Germany,
France, Sweden and Denmark, 50% or more of the
unrecycled waste is being or will be incinerated (Hjelmar, 1996). Incineration reduces the volume of the
waste by approximately 90% and allows for recovery of
much of energy bound in the waste. But when incinerating 1 ton of MSW, 300350 kg incinerator bottom
residue, 035 kg lter dust and 540 kg residue from
ue-gas purication system are produced (Schmelzer,
1995). The increasing incineration of MSW will produce
a considerable amount of MSW incineration (MSWI)
residues which must subsequently be utilised or landlled. For instance, in Japan and Germany, 6 and 3
million tons of MSWI residues are produced respectively each year (Sakai and Hiraoka, 2000; Pretz and
Meier-Kortwig, 2000). Over recent years, several studies
have been reported on the treatment, utilisation and
metal recovery from MSWI slag, mostly in Germany
and Japan.
4.1. Characteristics of MSWI residue
Depending on the MSW incinerated, the composition
of MSWI residues varies with the origins. Hjelmar
(1996) summarised the ranges of composition of some
MSWI bottom ash (excluding the scrap metal portion
and the size fraction larger than 45 mm) and y ash, as
shown in Table 16. From the results, it can be seen that
in the incineration process Fe and Cu mainly remain in

4500 C 24 h

Table 16
Composition of MSWI residues
Component

Unit

Bottom ash

Fly ash

Si
Al
Fe
Ca
Mg
K
Na
Ti
S
Cl
P
Mn
Ag
As
Ba
Be
Cd
Co
Cr
Cu
Hg
Mo
Ni
Pb
Se
Sn
Sr
V
W
Zn
PAH
CB
PCB
CP
PCDD
PCDF
TCDD
TOC
LOI

g/kg
g/kg
g/kg
g/kg
g/kg
g/kg
g/kg
g/kg
g/kg
g/kg
g/kg
g/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
g/kg
g/kg

210290
4772
27150
6597
7.719
9.222
2241
3.27.2
1.38
1.23.2
2.913
<0.71.7
4.114
1980
9002700
Nd
1.440
<1040
230600
9004800
<0.013
2.540
60190
13005400
0.68
<1001300
170350
3690
<2050
18006200
0.232200
6.745
<40
1634
0.210
0.444.5
0.020.22
4.813
5.950

95190
4978
1835
74130
1119
2347
2257
7.512
1132
45101
4.89.6
0.81.7
3195
49320
9201800
Nd
250450
2969
140530
8601400
0.87
1549
92240
740019000
6.131
14001900
<80250
32150
Nd
1900041000
30110
50890
<40
1201800
115140
4869
1.52.5
4.917
1145

TCDD: toxicity equivalents determined according to Eadons method.


Nd: no data available. PAH: polycyclic aromatic hydrocarbons. CB:
chlorobenzenes. CP: chlorophenols. PCDD: polychlorinated dibenzop-dioxins. PCDF: polychlorinated dibenzofurans. TOC: total organic
carbon. LOI: loss on ignition (550 C).

946

H. Shen, E. Forssberg / Waste Management 23 (2003) 933949

the bottom ash, whereas the volatile elements such as


Cd, Hg, As, Pb and Zn are enriched in the y ash. In
addition, y ash contains more PCDF, PCDD, CP and
CB and has a higher TCDD than bottom ash. Disposal
of bottom ash is considered less problematic than disposal of y ash. The potential recycling metals in the
bottom ash include Fe (27150 g/kg), Al (4772 g/kg),
Cu (0.94.8 g/kg), Pb (1.35.4 g/kg), Zn (1.86.2 g/kg),
Ti (3.27.2 g/kg), Sn (0.11.3 g/kg) and so on.
The material characterization study by Pretz and
Heier-Kortwig (2000) shows that MSWI slag contains
8590 wt.% mineral fraction, 15 wt.% non-incinerated
matter and 710 wt.% scrap metal. The mineral fraction
consists mainly of glass, ceramic, porcelain and heating
fuel ash, besides relatively large lumps of slag and
building rubble such as concrete, bricks and stones.
Partly or non-incinerated material comprises paper,
wood, plastic and textile components. The scrap metal
includes non-ferrous and ferrous (Fe) metals, such as tin
plate, aluminium, copper, brass, oil lter and water
taps. The thermal conditions during incineration lead to
a complete or partial melting and even to an oxidation
of the metal components. Surface intergrowth of melted
piece of scrap metals with mineral components are also
observed.
Incineration residues not only contain high content of
heavy metals, but also can release the heavy metals into
water when water leaches through the residues, especially through incineration y ash (Rhyner et al., 1995;
Sakai and Hiraoka, 2000; Hjelmar, 1996). In Japan, y
ash is classied as general wastes requiring special
controls (Sakai and Hiraoka, 2000). Therefore, further
treatment is necessary for incineration residues, particularly for y ash.
4.2. Recovery of metal from MSWI slag
Recovery of metals from MSWI residues closely
depends on the characteristics of MSWI residues and
the disposal strategy for MSWI residues. Since y ash
has high heavy metal and dioxin concentrations, it

needs special treatments, such as vitrication by remelting and extraction using acid or other solvents. For
bottom ash, two disposal strategies were reported. In
the rst, it is processed mechanically and then used, for
example, in the construction of streets, roads, and dams.
In the second, more secure treatment, it is pre-processed
mechanically and then treated with vitrication in which
the organic contaminants are destroyed and inorganic
contaminants are stabilised, namely by binding into
mineral matrix and by evaporation and collection in a
highly concentrated form as vitrication y ash. The
re-melted slag is used as a resource. In both treatments,
metal recovery from bottom ash is performed in the
mechanical processing stage. Metal recovery from vitrication y ash has also been reported.
Schmelzer (1995) reported a process for metal recovery from incineration bottom ash, as shown in Fig. 7.
The pilot operation results show that 62.6 wt.% processed ash, 35.5 wt.% magnetic material and 1.9 wt.%
non-ferrous material can be obtained from the bottom
ash. The magnetic material contains 2030% Fe. After
further processing with impact crushing, screening and
wet magnetic separation, ne scrap with 9095% Fe
and iron concentrate with 5055% Fe were produced.
The non-ferrous material mainly comprises Al, Cu, Zn
and other metals. By further wet gravity separation,
light product containing 95% Al and heavy product
with Cu 52.161.2%, Zn 25.236.5%, Pb 1.23.5%,
Sn 0.671.46% and Ag 02.0% were obtained
(Schmelzer et al., 1996).
A wet treatment reported for recovery of Pb and Zn
from vitrication y ash is shown in Fig. 8 (Sakai and
Hiraoka, 2000). The y ash is mixed with acid solution.
Zn and Cu are dissolved into the solution and separated from non-soluble Pb by ltration. Then, Zn and
Cu are changed into hydroxide through neutralization
and sulphured. After that Zn cake is obtained by ltration again. By this treatment, lead and zinc cakes
grading about 35% Pb and 31% Zn, respectively, are
produced from a vitrication y ash containing 3.14%
Pb and 6.86% Zn.

Fig. 7. Recovery of metals from incineration residue.

H. Shen, E. Forssberg / Waste Management 23 (2003) 933949

947

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

5. Conclusions
(1) A large amount of various slags are produced as byproducts in metallurgical processes or as residues in
incineration processes. According to the origins and the
characteristics, the main slags can be classied into three
categories, namely ferrous slag, non-ferrous slag and
incineration slag. They usually contain a quantity of
valuable metals except for BF slag. Recovery of metals
from the slags and uitilization of the slags not only can
save metal resource, but also can protect the environment.
(2) Ferrous slags mainly include iron slag, steel slag,
alloy steel slag and ferroalloy slag. Iron and steel slags
have comparable or even better properties than their
competitive materials for a range of applications. The
metals in iron and steel slags are tightly bound to the
slag matrix and not readily leached, and there are few
environmental concerns regarding their application.
They have been applied in many areas. BF slag contains
little metal and recovery of metal from it is not important. Steel slag is usually subjected to metal recovery
prior to its application outside the iron and steel making
process. By applying mineral processing technologies
such as crushing, grinding, classication and magnetic
separation, it is possible to produce steel scrap (Fe:
90%) and iron concentrate (Fe > 55%) from steel slag.
The amount of stainless steel slag is the largest among
the alloy steel slags and it contains high Cr and a certain
amount of Ni. Since stainless steel slag can release a
noticeable amount of Cr as high as 1 ppm and its leachate EC50 value exceeds the standard level of 3000 mg/
l, it may cause environmental concerns. It is desirable to
treat stainless steel slag prior to its application or even
landlling. Recovery of Cr and Ni from stainless steel
slag is not only cost-eective, but also very important
for the environment. Magnetic separation and gravity
separation methods were reported for recovery of Cr
and Ni from this slag, but few detailed papers were

released. It seems that more research work needs to be


done for the treatment of this slag.
Charge chrome slag is one of the ferroalloy slags.
More attention is focused on this slag since it contains
high content of Cr, usually 812%. Like stainless steel
slag, it also can release Cr into water and it may be harmful
to the environment. Magnetic separation method was used
for recovery of Cr from the slag, but up to date there has
been no commercial application. Gravity separation seems
more eective for separating Cr from this slag and it has
been applied in industry in India and South Africa.
(3) Non-ferrous slags usually contain heavy metals or
even toxic elements with a relatively high solubility.
There are relatively few reports on the application of
non-ferrous slags. The main work was focused on
recovery of metals from the slags. Among the non-ferrous slags, copper slag was subjected to the most extensive research work with a history of over 100 years. By
using otation, leaching or roasting, it is possible to
recover Cu, Co, Ni from copper slag. Beginning in the
1970s, attention was also paid to the treatment of salt
slag due to its rapid increase and its serious eect on the
environment. By mechanical separation and leaching
with water, Al metal pieces with 7% yield and salts with
50% yield can be obtained respectively from salt slag.
The remaining oxides become benign for landlling or
further application. In addition, recovery of Nb and Ta
from tin slag and Au and Ag from tin slag and other
slags were also performed.
(4) Incineration slag (or residue) is a relatively new
ever-increasing slag. Since incineration y ash has high
heavy metal and dioxin concentrations, it needs special
treatments, such as vitrication by re-melting, extraction using acid or other solvents and so on. Separation
of metals from incineration bottom ash has been
applied in industry. Fe, Al, and Cu etc. can be obtained
from bottom ash by mechanical separation incorporating drying, crushing, sieving, magnetic separation and

948

H. Shen, E. Forssberg / Waste Management 23 (2003) 933949

eddy current separation. After mechanical processing,


the bottom ash was reported being used in the construction of roads and dams. But the more secure disposal strategy is to melt the processed bottom ash at
approximately 12001400 C (called vitrication) to
make the ash stable and non-toxic so as to use it as a
resource, e.g. construction materials. Recovery of
metals is also performed from vitrication y ash. For
example, Pb and Zn concentrates can be obtained by
the hydrometallurgical method.

Acknowledgements
The authors are grateful to the Minerals and Metals
Recycling Research Center, Lulea University of Technology, Sweden, for nancial support and approval of
this paper for publication.

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