Copyright

c 2012
Department of Process and Environmental Engineering
Editor in Chief: Riitta Keiski
Publisher: University of Oulu, Faculty of Technology, Department of Process and Environ-
mental Engineering
Place of publication: Oulu
Serie founded: 1979
Former: University of Oulu, Department of Process and Environmental Engineering. ISBN
978-951-42-9832-5
Cover: An aerial view of ThyssenKrupp steelworks in Duisburg, Germany. (AP Photo/Frank
Augstein)

UDK 669.118
ISBN 978-951-42-9832-5
ISSN 1458-6177

UNIPRINT
OULU 2012
University of Oulu
Department of Process and Environmental Engineering
Laboratory of Process Metallurgy
2
Abstract
Matti Aula, Juho Haapakangas, Anne Heikkilä, Mikko Iljana, Antti Kemppainen, Juha
Roininen, Petri Sulasalmi and Ville-Valtteri Visuri. Some Environmental Aspects of BF,
EAF and BOF
Department of Process and Environmental Engineering. PO Box 4300, FI-90014 University of
Oulu, Finland
Layout: Anne Heikkilä and Ville-Valtteri Visuri

This report is a compilation work of the papers prepared for the Postgraduate Seminar in
Process Metallurgy held in Spring 2012. The seminar considered the environmental effects of
the main unit operations in conventional steelmaking process route. This report provides an
extensive a literature review of the formation and reuse of dust and slag in Blast furnace, Electric
Arc Furnace and Basic Oxygen Furnace processes. The report can be used as a basis for further
literature research.

3
4
Contents
Abstract
Contents 5
1 Introduction 7
1.1 Slags in steelmaking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.2 Preprocessing of dust and sludge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2 Environmental aspects of blast furnace slag, dust and CO2 emissions 11
2.1 Blast furnace slag . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.1.1 Blast furnace slag formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.1.2 Tapping the furnace . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.1.3 Blast furnace slag disposal and structure . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.1.4 Blast furnace slag utilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.1.5 Utilization of granulated blast furnace slag in cement industry . . . . . 16
2.1.6 Alternative ways to use blast furnace slag . . . . . . . . . . . . . . . . . . . . . . . 19
2.2 Dust and sludges from blast furnace process . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.2.1 Off-gas cleaning system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.2.2 Formation of off-gas dust. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .26
2.2.3 Treatment and utilization of BF dust and sludge . . . . . . . . . . . . . . . . . . 30
2.3 CO2 Emissions from Blast Furnace Ironmaking . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.3.1 The present state . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.3.2 Future technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.3.3 Efforts to reduce blast furnace CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
2.3.4 Challenges related CO2 reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
3 Environmental aspects of EAF slag, dust and off-gas 43
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.2 EAF slag practice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.2.1 Slag in different processing periods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.2.2 About phosphorous and sulfur removal . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.2.3 Slag foaming in EAF processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
3.2.4 Tapping of the process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.2.5 Utilization of the slag from EAF processing . . . . . . . . . . . . . . . . . . . . . . 52

5
 3.3 Environmental aspects of electric arc furnace dust . . . . . . . . . . . . . . . . . . . . . . . 53
3.3.1 Characteristics of EAF dust. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .54
3.3.2 Dust generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
3.3.3 Preventing dust generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.3.4 Disposal of EAF dust . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.3.5 Recycling back to EAF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.3.6 Reprocessing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.3.7 Disposal to landfill. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .57
3.4 Environmental aspects of EAF off-gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
3.4.1 CO and CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
3.4.2 NOx , VOCs and dioxins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
4 Environmental aspects of BOF slag and dust 61
4.1 Basic oxygen furnace . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
4.2 Basic oxygen furnace slag . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
4.2.1 Production and environmental concerns . . . . . . . . . . . . . . . . . . . . . . . . . . 63
4.2.2 Use in civil engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
4.2.3 Use in water treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
4.3 Basic oxygen furnace dust . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
4.3.1 Dust formation mechanisms in BOF process . . . . . . . . . . . . . . . . . . . . . 69
4.3.2 Composition of BOF dust . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
4.3.3 Pre-processing methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
4.3.4 Recovery of Zn and Pb . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.3.5 Removal of alkalis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75

6
1 Introduction
This work is a product of a postgraduate course during spring 2012. The subject is
environmental aspects of some byproducts in steelmaking industry. Topic here consists
of blast furnace, electric arc furnace and basic oxygen furnace. And more presicely
in the environmental aspects of their slag, dust and off-gas. The discussion focuses
more on the ”what is” aspect rather than ”what will be”. Main problems concerning the
handling of said byproducts as well as ways to deal with them are presented.

1.1 Slags in steelmaking

As illustrated in Figure 1, the main categories of slag in steelmaking are

1. Blast furnace slag

2. Electric arc furnace slag
3. Basic oxygen furnace slag, and
4. Secondary metallurgy slags.

In the process of making steel, slag is one of the occuring byproducts. For example
when making crude iron a liquid silicate melt is formed from the impurities and fluxing
agents on top of the liquid crude iron. This silicate melt is called slag. Slag has multiple
purposes such as serving as a place for the impurities removed from the liquid iron and
protecting the iron from re-oxidating. When slag has solified it has different uses. Of
course these depend from the attributes of said slag (Oss 2003). Different uses for slags
are discussed later as well as their main problems.

1.2 Preprocessing of dust and sludge

Significant quantities of dust, sludge and slag are generated as waste material or byprod-
uct every day from steel industries. They usually contain considerable quantities of
valuable metals and materials. It is generally possible to recover some values by physical
or chemical mineral processing techniques such as crushing, grinding, classification,
hydrocyclone, magnetic separation, flotation, leaching or roasting. Transforming these
solid wastes from one form to another to be reused either by the same production unit or
by different industrial installation is very much essential not only for conserving metals

7
Fig 1. Slags in steelmaking (Eisenhüttenschlacken e. V Forschungsgemeinschaft
2012), translated from German by V.-V. Visuri
and mineral resources but also for protecting the environment (Das et al. 2007b).
When it comes to recycling the dust as a raw material for steel, consideration must be
given to the limitations set by the individual processes (blast furnace, converter, electric
furnace, etc.) that are likely to use the product made from recycled dust. When the
product is used in a blast furnace, for example, low zinc concentration and high strength
matter most. When it is used in a converter or electric furnace, sulfur concentration and
metallization ratio are especially important. Figure 2 clarifies the problems to be solved
when dust is recycled to different processes (Oda et al. 2006). Methods range from
simple agglomeration techniques to new hot metal production processes for treating
the dust materials which are useful in pretreating the waste materials to make them
more amenable to recycling in iron and steel making operations. Preprocessing involve
thermal, hydrometallurgical and physical beneficiation methods.

8
Fig 2. Problems to be solved in dust treatment (Oda et al. 2006)

9
10
2 Environmental aspects of blast furnace slag,
dust and CO2 emissions
Authors: Juho Haapakangas, Anne Heikkilä, Mikko Iljana and Antti Kemppainen

2.1 Blast furnace slag

2.1.1 Blast furnace slag formation

A blast furnace process remains by far the most important process for the production of
pig iron. The blast furnace slag (BFS) is the by-product released from blast furnace. The
blast furnace is a closed system into which iron bearing materials (iron ore lump, sinter
and/or pellets), additives (slag formers such as limestone or dolomite) and reducing
agents (coke) are continuously fed from the top of the shaft furnace. A hot air blast
enriched with oxygen and auxiliary reducing agents is injected and the air blast reacts
with the reducing agents to produce mainly carbon monoxide, which in turn reduces
iron oxides to metal iron. Fluxes and additives are added to lower the melting point of
the gangue, improve sulphur uptake by slag, provide the required liquid pig iron quality
and allow further processing of the slag. When the metallurgical smelting process is
complete, the lime in the flux has been chemically combined with the aluminates and
silicates of the ore and coke ash to form a non-metallic product called BFS. The main
chemical composition includes CaO, SiO2 and Al2 O3 . In addition, it contains very little
MgO, FeO, and a little sulfide, such as CaS, MnS, and FeS. During the period of cooling
and hardening from its molten state, BFS can be cooled in several ways to form any of
several types of BFS products. For further processing it has to comply with special
quality demands. Therefore in modern blast furnaces the operation mode is carried out
with regard to the quality of the pig iron and the blast furnace slag. (Fu et al. 2000)

2.1.2 Tapping the furnace

The operation of a blast furnace is a continuous process, and the furnace continues to
produce liquid iron and slag as long as it is in operation. The iron and slag accumulate
in the hearth, but because there is a limit to the amount that can be tolerated before

11
it interferes with the furnace operation, the slag and iron must be removed from the
furnace at regular intervals. The iron notch, which is used for tapping the hot metal from
the furnace, is located slightly above the floor of the hearth. Most modern furnaces are
equipped with more than one iron notch. There is also a cinder notch for removing
slag from the furnace, and it is located in a plane typically 1-2 m above the iron notch.
Before the blast furnace burdens were improved to today’s current standards, the weight
of slag produced in the blast furnace was more than half the weight of the hot metal.
The lower density of the slag caused it to fill up the space in the hearth above the metal,
and it would interfere with the penetration of the blast air and the combustion process at
the tuyeres long before the accumulation of iron had reached the desired amount for
casting. Consequently, it was necessary to remove the excess slag through the cinder
notch (generally referred to as the monkey) once or twice between casts. However,
in recent years, since better prepared burdens have been used, the slag volumes have
decreased to 200-300 kg/ton. Therefore the monkey is seldom used and the slag is
typically only removed via the iron notch during the casting process. (Wang et al. 1999)

2.1.3 Blast furnace slag disposal and structure

BFS is handled in many different ways, depending upon the amount of space available
around the furnace and on the type of product that is to be made from the slag. At most
of the older blast furnaces, the slag was run into cinder pots mounted on railroad cars
and transported outside the plant to a slag dump. The cinder pots (also called slag pots)
are unlined, thimble shaped, cast iron or steel castings mounted on railroad cars. The pot
fits into a bracket with trunnion mountings set on a rack and pinion so that it they can be
rotated and dumped by a compressed air operated cylinder mounted on the railroad
car. The slag from the pots can be dumped over a bank into pits and later excavated,
crushed and screened to be used as ballast or aggregate. Or the slag can be poured into
the path of a high pressure stream of water that expands it into popcorn like material to
be used as lightweight aggregate. At many modern blast furnaces, the slag is run into
pits adjacent to the casthouse. There are usually two pits so that one can be excavated
while the other is being filled. It usually requires two or three days to fill a pit, and after
each run of slag water sprays are used to assure that the slag will solidify rapidly enough
to be ready for excavating on schedule. At several blast furnaces, the slag runner directs
the slag in front of high pressure water sprays that granulate it into small pieces and
then wash it into a wet pit. The rapid cooling of the slag gives it a glassy structure,

12
and when it is finely ground, it has hydraulic bonding properties and can be used in
cement. Similarly, a few furnaces have been equipped with machines to form pelletized,
lightweight slag granules. In these installations, the molten slag is diverted from the slag
runner to water-cooled, rotating drums which throw the slag through the air onto a pile
a short distance from the machines. The slag is rapidly cooled by the water used as
external coolant for the drums and by the air while it is in flight. The cooled slag is
similar in properties to the granulated slag except the particles are more spherical in
shape. Blast furnace slag crystallization according to cooling conditions on is shown in
Table 1. (Wang et al. 1999)

Table 1. Processing methods for blast furnace slag. (Gara 1998)

Treatment Structure Kind of slag

Slow cooling on air Crystalline Air cooled blast furnace slag

(lump slag, rock slag)

Very fast cooling Vitreous, Granulated blast furnace

with water in amorphous slag (GBS) (granulated cinder)
granulation plants

Middle cooling in High porous, Expanded blast furnace

combination with vitreous/ slag (foamed blast furnace
directed induced gases crystalline slag)

Jet air or Fibrous, Mineral wool, slag wool

water vapour vitreous

Fluid slag flows Fine fraction: Blast furnace pellets

on water-cooled almost vitreous; (pelletized blast
rotating roll coarse fraction: furnace slag)
vitreous/crystalline

2.1.4 Blast furnace slag utilization

Two types of blast furnace slag such air-cooled slag and granulated slag are being
generated from the steel plants. The air-cooled slag is used as aggregates in road making
while the granulated slag is used for cement manufacturing. This has been fully utilized

13
throughout the world. In Figure 3 are shown the results of the survey performed in
2008 for European steelworks and processing companies for production of different
slag types and for use of slag. Total blast furnace slag amounts were 28.1 million tons
for production and 30.3 million tons for use in Europe in 2008. Annual blast furnace
slag production in European countries is approximately: Germany 7-8 mt/a, France
about 4 mt/a, United Kingdom about 2 mt/a, Austria, Finland, Sweden, Netherlands and
Belgium Flemish Region 0.5-2 mt/a. The other European countries have smaller or not
specified BFS production amounts. (Euroslag 2008)

Fig 3. Production and use of blast furnace slag in Europe in 2008. (Euroslag 2008)

It has been proved that around 50 % of clinker is replaced by additives like blast
furnace granulated slag in the production of cement. Apart from the proven benefits
in cement quality such as low heat of hydration, good long term strength, control of
alkali-silica reaction, resistance to acid, better durability by the addition of granulated
slag, it is also a cost saving measure to the cement industries. (Das et al. 2007a)
The BFS can be also used in the preparation of materials such as ceramic glass, silica
gel, ceramic tiles, bricks, etc. It was shown that a glass-ceramic route can be successfully
applied to the blast furnace slag with the aim of converting it into useful product. The
devitrification behavior of different sizes of slag-derived glass was investigated using

14
differential analytical techniques to determine the possibility of preparing glass-ceramic
materials. The crystalline phases of slag were identified as gehlenite, diopside pyroxene
and barium aluminium silicate. The difference in the glass-ceramic texture was observed
by treating the sample at different crystallization temperatures. Both acicular and
dendritic morphology have been identified in the sample heat-treated at 1050 ◦ C. A
slight variation in peak crystallization temperature with particle size indicated a bulk
crystallization mechanism. (Francis 2004)
The recovery of silica gel from blast furnace slag has been attempted by leaching
with H2 SO4 , separation of gypsum, precipitation of silica gel at pH 3.2, followed by the
washing of the raw precipitate (Seggiani & Sandra 2002).
The ceramic tiles were prepared from granulated blast furnace slag and common
clay by mixing calcia-silica ratio at different proportions. The optimum compositions
were found to be where calcia-silica ratio were in the range of 0.1-0.3. Formation of
wollastonite in the sintered compacts with finer grain size was found to be an important
parameter for increase in strength. (Ghosh et al. 2002)
Crystalline and amorphous blast furnace slag can be used as an adsorbent of
phosphate from water solutions. The adsorption kinetics measurements confirmed
that a model involving pseudo-second-order reactions could describe the sorption of
phosphorus on crystalline as well as amorphous slags. The phosphorus sorption follows
the Langmuir adsorption isotherm (Kostura et al. 2005).
The adsorption characteristics of blast furnace slag on the removal of lead have
been investigated as a function of pH, the metal ion concentration, the particle size and
the amount of sorbent. It has been established that the process occurs with increasing
pH and the efficient lead removal by granulated slag occurs at pH values lower than
precipitation pH values. The equilibrium in the slag lead solution system is described by
the Freundlich adsorption isotherm. The percentage of lead removal at equilibrium
increases with increasing slag amount but the sorption capacity decreases. Depending
on the conditions, a percent lead removal of 97-98 % can be achieved. The results
obtained could be useful for the application of granulated slag for the Pb ions removal
from industrial waste (Dimitrova & Mehandgie 1996).

15
2.1.5 Utilization of granulated blast furnace slag in cement
industry

Today BFS has found a wide application in cement production and marketed as Portland
blast furnace slag cement (PBFS). The ground granulated blast furnace slag (GGBFS)
has been widely used in Europe, and increasingly in the United States and in Asia
(particularly in Japan and Singapore) for its superiority in concrete durability, extending
the lifespan of buildings from fifty years to a hundred years. Since blast furnace slag
contains little iron and high calcium oxide content with similar composition of clinker, it
can be safely used along with the clinker and gypsum for production of cement. The
chemical and mineralogical composition of granulated blast furnace slag in and ordinary
Portland cement clinker (OPCC) are shown in Table 2 .

Table 2. Chemical composition of granulated blast furnace (GBS) slag in compari-

son with ordinary Portland cement clinker (OPCC). (Böhmer et al. 2008a)

Component BGS OPCC

Insoluble residue 0.03 - 4.06 0.04 - 0.72
SiO2 30.5-40.8 19.8-23.4
Al2 O3 5.9-17.6 4.0-6.5
FeO 0.12-4.72 -
Fe2 O3 - 1.5-3.8
TiO2 0.07-3.70 0.13-0.30
MnO 0.07-3.12 -
Mn2 O3 - 0.01-0.28
CaOtotal 30.9-46.1 64.1-68.4
CaOfree - 0.30-2.37
MgO 1.66-17.31 0.72-4.66
Na2 O 0.09-1.73 0.03-0.38
K2 O 0.08-1.51 0.37-1.30
Na2 O-Equivalent(Na2 O+0.658*K2 O) 0.19-2.61 0.47-1.07
SO2−
3 0.00-0.86 0.14-1.84
S2− 0.42-2.29 -

Currently, there is high interest in the application of this alternative material because
the production of Portland cement clinker contributes about 5% to the global man-made

16
CO2 emissions. Despite the fact that the amount of available slag is limited, there is an
increasing demand for slag cement to reduce the CO2 emissions due to the production of
cement and concrete. (Lukasik et al. 2007)
The blast furnace slag used in the cement production is GGBFS. The use of GGBFS
as a cement replacement, in addition to the ecological and environmental benefits has
considerable advantages and some disadvantages when compared to the performance of
conventional ordinary Portland cement (OPC) concrete.
When GGBFS is used as cement replacement, one improvement is the compressive
strength due in part to the fineness of the GGBFS and to the chemical hydration GGBFS,
which is latently hydraulic, undergoes hydration reactions in the presence of water
and calcium hydroxide Ca(OH)2 . This secondary pozzolanic reaction yields a denser
microstructure because the Ca(OH)2 is consumed and CSH paste is formed. Another
benefit of using mineral admixtures, which leads to an increase in strength development,
is due to heterogeneous nucleation. This process enhances the chemical activation of the
hydration of cement. Thus, increasing the amount of the mineral admixture and refining
its particle size will promote heterogeneous nucleation due to the availability of sites.
Compressive strength gain of concrete has been attributed to the degree of hydration and
porosity.
Although the hydration kinetics of concrete containing GGBFS is not yet fully
understood, it has been shown that the rate of hydration of concrete containing GGBFS
compared to OPC concrete is slower. As a result, the recommended curing period
for concrete containing GGBFS is generally 7 days in comparison to 3 days for OPC
concrete. However, what is not clear, are the implication of the hydration kinetics on the
mechanical properties and other properties of concrete products at 28 days. Especially
when published reports show that by 28 days, only 18-55% of the GGBFS used as
cement replacement has reacted. One reported disadvantage of concrete containing
high percentages of GGBFS as cement replacement in comparison to OPC concrete is
lower resistance to deicing salt scaling when tested at 28 days. It has been proposed
that the substitution of GGBFS should be limited to 25 % in concretes which will be
exposed to deicing salts. The reasons for the poorer performance are not clear. However,
some researchers have partially attributed it to the slow hydration and insufficient
curing regime for concrete containing GGBFS. This implies that the evaluation of the
scaling resistance of GGBFS concrete a 28 days is partially influenced by the relatively
slower rate of hydration and curing period. For methods to increase the GGBFS cement
strength properties and resistance to scaling after 28 days researchers have suggested

17
fine grinding and use of alkali activation. (Chidiac & Panesar 2008)
It has been shown the replacement of cement clinker by GGBFS usually results in
lower early strength and longer setting times, and restricts the use of large proportion of
slag in Portland slag cement. Fine grinding and mechanical activation has been suggested
to improve the reactivity of the blended cement constituents. Fine grinding leads to
generation of larger surface area, whereas mechanical activation results from combined
effect of particle breakage (surface area) and other bulk and surface physicochemical
changes, dislocations and other defects induced by the milling. Due to enhanced
reactivity, the resulting cement and/or concrete exhibits improved strength and setting
properties. Researchers have shown that with attrition mills, also known as stirred ball
mills it was observed that complete hydration of the slag is possible without a chemical
activator if the slag is mechanically activated after 28 days, without any chemical or
clinker addition. (Kumar et al. 2008)
Especially the use large amount of slag as a replacement of OPC has attracted
significant research attention worldwide and it has been proposed that to optimize the
properties of cement containing a large amount slag the proper formula for mixtures
with high amount of slag are detailed as follows: clinker 30-50%, slag 45-65%, activator
6-8%. (Fu et al. 2000)
Experiments made with alkali activated relatively coarse BFS have shown that for
activation of BFS with Na2O the required amount of Na2 O is around 6% relative to the
slag weight to obtain the sufficient 28 days strength for concrete. Higher Na2 O contents
increased strength marginally and would increase the cost; whereas lower contents
develop poor strength after 28 days. Aspect that also needs to be taken in consideration
is that the concretes based on activated slag are of lower environmental impact, since the
slag does not require thermal processing and there is no decarbonation of CaCO3 as in
Portland cement. The slag is more resistant to grinding than Portland cement, a coarser
particle size contributes to reduce costs too.(Escalante-Garcia et al. 2009)
Blast furnace slag is usually activated by mixing with Portland cement clinker. At
very high pH values (13.0) corrosion of the slag particles is enhanced and the reaction of
blast furnace slag is accelerated. Researchers have shown that activation of the slag is
also possible at low pH values (11.8-12.4) by using the addition of calcium hydroxide
and soluble calcium salts. These methods can be applied to improve the performance of
slag cements containing very high amounts of slag. (Bellmann & Stark 2009)
As a conclusion it seems so far that the sufficient strength and resistance properties
for the concrete can be achieved even with large amount of granulated blast furnace slag

18
as cement replacement with different activation methods or with sufficiently long curing
time periods. Depending on the material and handling costs, environmental aspects and
resistance requirements the fabrication method can be selected from among these.

2.1.6 Alternative ways to use blast furnace slag

Slag as a basal media for eelgrass bed

Eelgrass (Zostera marina L.) is a temperate marine angiosperm and considered to be a

key inhabitant of the coastal zone. Eelgrass beds are considered to play important role in
many marine systems. Eelgrass beds have been lost due to natural causes and human
activities.
The use of an artificial basal media (made from blast furnace slag, BFS) in restoring
the eelgrass habitats has been studied. Two different BFS types were used in experiments,
granulated slag (GS) and air-cooled slag (ACS). These were compared to the natural
eelgrass sediments (NES) in terms of physic-chemical characteristics. It was found that
particle sizes of GS and ACS were sufficient for growing eelgrass. Though ACS had low
silt-clay content and both BFS samples had lack of organic matter content. Still it was
possible for the eelgrass to survive in the BFS substrates, but the growth rate was slower
than in NES. Possible causes for this stunned growth could be speculated to be the lack
of organic matter and release of some possible toxins from BFS. Thus an experiment
was made to try to reduce the S content on the slag samples. The samples were washed,
but this did not improve their ability to act as eelgrass substrate. Although no sulfide
was released from the slag samples anymore, other phytotoxins, especially Zn, release
increased in alarming amounts after S reduction.
It has been shown that it is possible to use BFS as a substrate for eelgrass beds, but
the right treatment for BFS should be found so it could be considered effective material
for such utilization. (Hizon-Fradejas et al. 2009)

Sand made from slag

The amount of available natural sand is decreasing every year. The sand has been used
for example in sand-capping which is a marine environment improvement technology.
The organic sea-bottom sediments are covered with layer of sand in order to reduce the
elution of nutrient salts that causes eutrophication of seawater, and hydrogen sulfide that

19
causes blue tides. Since excavation of natural sand causes environmental issues, new
materials for sand-capping has been sought.
Blast furnace (BF) slag can be transformed in to granulated BF slag sand. When
comparing the granulated BF slag sand with beach sand examples from both were
laid over bottom sediment. It was found that BF slag sand was better suppressing the
generation of hydrogen sulfide than that of beach sand. Then black acrylic containers
were placed on top of the BF slag sand which was laid at the bottom sediment. Silicate
concentrations were measured and area where BF slag sand was laid had higher
concentration than area where bottom sediment was exposed. Thus it was concluded
that BF slag sand has the effect of feeding silicate to seawater. A certain silicate
concentration is required for the primary food source for many organisms living in
the sea, diatoms, to grow. It was also observed that various marine organisms were
living in the area where BF slag sand was laid over the bottom sediment. Actually more
organisms lived at the BF slag sand covered area than just sediment-covered area.
Another application for BF slag is to form it to cubes and solidify them by injecting
CO2 . These cubes are called Marine Blocks. An experiment was started at the end of
the year 1997 when 25-cm-cube slag blocks were places on the bottom of the Inland
Sea. During summer 1998 it was found that green marine plants were proliferating
on the slag cubes. Same types of marine plants were grown on natural stones which
were scattered around the slag cubes. This indicates the effect slag cubes have on the
surrounding sea bottom. (Takahashi & Yabuta 2002)

Possible use of slag as a catalyst

Large-scale wastes may have a purpose serving in catalysis process. Even though this
does not remove the disposal problems it may provide an inexpensive route to active
systems. There are many approaches to the use of large-scale waste in this context for
example direct application as active material, direct use as pre-catalysts, modification
such that it yields catalytically active phases and being precursor for the synthesis of
active catalyst.
Large-scale wastes can be roughly divided into two groups: industrial wastes and
biological wastes. Blast furnace and steel slags are major industrial waste products.
The global production of slag in 2008 was within range of 240-290 million tons. The
typical composition of raw blast furnace slag is CaO 40.09 wt%, SiO2 34.58 wt%,
Al2 O3 14.78 wt%, MgO 5.29 wt%, Fe2 O3 1.53 wt%, TiO2 0.78 wt% and MnO 0.27

20
wt%. The presence of CaO is problematic in the sense that materials containing excess
of 15 wt% CaO are unsuitable for zeolite synthesis because of the forming calcium
silicate. The zeolite nucleation is inhibited by formed calcium silicate. This problem
may be circumvented by an alternative acid treatment where the undesirable components
for zeolite synthesis are eliminated.
The importance of using the large-scale wastes lies in the availability of low cost
alternative for the existing catalysts or as precursor in their preparation. The goal
is to find the balance between economics of any associated activity differences and
processing costs. (Balakrishnan et al. 2011)

Formation of slag into glass-ceramic material

Glass-ceramics are materials processed from glasses via subsequent heat treatment.
During this heat treatment the glass converts into a crystalline ceramic. Especially
for glass derived from blast furnace slag the main use is believed to be in the form of
pipes and tiles for the conveyance and storage of abrasive materials. Glass-ceramics is
much more resistant to abrasion when compared to alternative metals and alloys. It
is possible to apply the glass-ceramic route to blast furnace slag thus converting it to
useable product. (Francis 2004)

Monitoring the consequences of slag dumping

A framework has been established for the protection of groundwater, inland surface
waters, estuarine (=transitional) water and coastal waters by the European Water
Framework Directive (WFD). Its main objective is to achieve ’good ecological status for
all waters by 2015. Member States are developing monitoring programs for water status
monitoring. There are three types of monitoring programs: surveillance monitoring,
operational monitoring and investigative monitoring.
There is a case study area which was Basque coast (northern Spain) where metal-
containing slags from the blast furnace has been disposed at throughout the 20th century.
The purpose of the study was to determine is the slag dumped until 1996 can represent a
problem in the future.
From the previous monitoring it is known that the metal concentration of the
sediments on the dumpsite is several times over the background levels defined previously
for the region. In this particular case-study the investigative monitoring attempts were

21
to pinpoint the exceedances of quality objectives in metal content, to validate if there
was a risk, determinate the extent of the alleged problem and to examine the impact on
biological communities.
It was found that after 12 years the slag dumping along the coastal area has not
produced toxicological or harmful effects in the biota. It would also seem that dispersion
and dilution of the materials with low bioavailability do not portray a risk in achieving
good ecological status. (Borja et al. 2008)

2.2 Dust and sludges from blast furnace process

There are many dust sources in ironmaking. Firstly, some dust is generated in the
stockhouse while screening the charge materials. Secondly, some dust is collected in the
casthouse from the taphole, the skimmer, the casthouse top and when running hot metal
and slag to ladles. Thirdly, ascending gases take fine particles with blowing out from the
top of the blast furnace. Fourthly, some dust is generated in desulhurization plant while
adding limestone to hot metal. The dust from desulphurization is sulphur and alkali rich
preventing its utilization. This chapter focuses on the off-gas dust leaving the BF top.
Particles which are blown out from the top of the blast furnace with the ascending
gases cause material losses. In order to reduce these losses, it is important to understand
the off-gas formation. The blast furnace gas leaving the top of the furnace contains
solid particles varying in size from about 6 mm to only a few micrometers. The dust
carried out of the top of the blast furnace in the gas stream is referred as off-gas dust.
The off-gas dust is a mixture of oxides consisting mainly of iron oxides and coke fines.
It also contains silicon, calcium, magnesium and other minor elemental oxides in lesser
amounts. Fines accumulation in the shaft of the BF decreases gas permeability, changes
the gas flow and therefore will possibly affect generation of dust due to channeling in
the burden. (Das et al. 2007a, Wakelin 1999, Lundgren et al. 2011)
Generally, off-gas dust cannot be recycled directly because of some undesirable
elements (zinc, alkali metals, lead, sulphur, cadmium, cyanides etc.). Alkaline elements
(sodium and potassium) and zinc accumulate in the blast furnace burden due to cyclic
reactions and that’s why alkali and zinc input to the blast furnace must be limited. Zinc
has been regarded as a problem because the zinc circuit leads to extra coke consumption.
Alkaline elements can cause operational difficulties in the blast furnace like the loss of
permeability of the burden and cracking of refractory bricks or unacceptable hot metal
composition. (Das et al. 2007a, Wakelin 1999, Lundgren et al. 2011)

22
2.2.1 Off-gas cleaning system

The blast furnace off-gas must be cleaned before it can be utilized in heat production
which mainly is executed as burning in the hot blast stoves. The cleaning of blast
furnace gas occurs in two stages. In the primary cleaning system, the coarsest fraction is
segregated in dry separation and after that the fines go along to the secondary treatment
which can be processed either under wet or dry conditions. Traditionally, a gravity dust
catcher acts as primary treatment but nowadays cyclones and a combination of a dust
catcher and a cyclone have become general. (Wakelin 1999, Majdalani & Rienstra 2007,
Stalinskii et al. 2008) Figure 4 presents the general blast furnace gas cleaning system
with a dust catcher and secondary gas cleaning system under wet conditions.

Fig 4. General arrangement of blast furnace primary gas cleaning equipment

(Wakelin 1999).

Primary cleaning system

As stated earlier, a dust catcher is a traditional primary cleaning system of blast furnace
off-gas dust. It is a large clarifier chamber with diameter about 10-12 m and height
20-30 m. The gas enters the dust catcher through the top by a vertical pipe that carries
the gas downward inside the dust catcher. This pipe flares outward at its lower extremity
so that gas loses its velocity when passing downward. The gas outlet is near the top
and the bottom is closed, so the gas must reverse 180◦ its direction whereupon coarse

23
particles drops to the dust catcher bottom. The efficiency of dust removal depends on the
size of the dust particles and the ratio of the gas velocity to the size of the dust catcher.
The dust that accumulates in the dust catcher is removed periodically. Generally, the
extraction efficiency of a dust catcher is 40-60%. (Wakelin 1999, Streit 2007) Figure 5
shows a schematic picture of a dust catcher and a venturi washer. The venturi washer is
a part of secondary cleaning system.

Fig 5. Schematic picture of a dust catcher and a venturi washer (Wakelin 1999).

However, the dust catcher is not the best available technique for primary blast
furnace off-gas cleaning. The extraction efficiency of an axial cyclone is much better
compared to a dust catcher’s. A cyclone is an expensive investment while existing
primary cleaning equipment and gas lines must be dismantled. (Sperkach et al. 2008)
Figure 6 a) shows the operational principle of an axial cyclone. In a blast furnace gas
cleaning system with an axial cyclone (see Figure 6 b), the gas is supplied to the cyclone
in two gas lines and the gas flow is directed by special blades to the peripheral zone in
the cylindrical part of the apparatus. When achieving the bottom of the cyclone, the gas
flow is directed upwards and leaves the cyclone in the top part. Large-sized particles are
separated to the bottom of the cyclone to a dust collecting chamber but the finest fraction
goes on with the gas flow. This construction ensures highly efficient dust separation,
significantly increases the amount of reusable iron and carbon-bearing raw material
obtained and decreases the amount of wet sludge. The extraction efficiency of a cyclone
rises up to 70-85% being significantly better than the dust catcher’s. Additionally, the
extraction efficiency of a cyclone can be controlled in relation to operation conditions of

24
the blast furnace. (Sperkach et al. 2008, Suvorov 2009)

Fig 6. (a) Operational principle of an axial cyclone (Majdalani & Rienstra 2007). (b)
Schematic diagram of the axial cyclone in the dry-type gas cleaning system of a
blast furnace (Suvorov 2009).

Additionally, a combination of a dust catcher and a cyclone (see Figure 7) is

a common and effective technical solution to decrease the amount of wet sludge.
Stalinskii et al. estimate that the installation of an additional cyclone increases the
extraction efficiency of dry dust from 50-55% to 75-77% and halves the amount of
sludge. (Stalinskii et al. 2008) The extraction efficiency of this kind of a combination
is somewhat same as a cyclone by oneself but the implementation of a dust catcher -
cyclone combination is significantly quicker compared to dismantling the current dust
catcher and installing a new cyclone based gas cleaning system (Sperkach et al. 2008,
Meriläinen 2012)

Secondary cleaning system

The dust passing through the dry primary cleaning system generally goes to the wet
secondary cleaning system where the very fine particles of dust are separated out of the
gas with water. A venturi washer is a traditional wet gas cleaning equipment. In the
venturi washer, gas passes through a narrow throat in which it is sprayed with water.
The water used in the secondary cleaning is rich in solids and in order to use that water
in a closed loop circuit these solids must be separated. The output of the secondary

25
Fig 7. Combination of a dust catcher and a cyclone. (1) dust catcher, (2) cyclone
and (3) dust output. (Stalinskii et al. 2008)
cleaning system is wet sludge containing 30-50 wt% of the total dust removed from the
gas. (Wakelin 1999)

Off-gas cleaning plant at Ruukki Raahe Steel Works

At Raahe Steel Works, the blast furnace gas goes to a dust catcher as primary treatment.
The overflow goes along to a scrubber, a venturi scrubber and a droplet separator
comprising the secondary treatment and after that the cleaned gas can be utilized in heat
production. The water used in secondary treatment is led to the clarifiers via the sludge
channel. The underflow of clarifiers is led to the centrifuges in which sludge is dried to
approximately 30 wt% moisture content. The dried sludge is not recycled to the process
because of a high concentration of some harmful elements (especially zinc) and is stored
in an intermediate storage. (Meriläinen 2012)

2.2.2 Formation of off-gas dust

Off-gas dust is formed either mechanically from abraded charge material particles that
are transported with the process gas or in chemical reactions within the blast furnace
by vaporization followed by condensation from the process gas at lower temperatures
(circulating elements). Mechanically formed dust has coarser diversified particle size
compared to chemically formed dust which has a particle size of approximately 1 µm.
(Wakelin 1999, Lundgren et al. 2011, Leimalm et al. 2010)
Pipatmanomai et al. pinpoint that the blast furnace off-gas dust include also fine
injectant coal particles and soot. The high rates of coal injection are associated with

26
soot formation causing reductions in coke bed porosity and high dust emission rates.
(Pipatmanomai et al. 2004) Leimalm et al. has studied EBF off-gas dust and they
have concluded that flue dust is mechanically formed and sludge chemically formed
(Leimalm et al. 2010). Kallio has also studied dust samples collected from dust catchers
in the LKAB’s experimental blast furnace (EBF) and according to his research results,
coarse-grained dust is generated during charging as the mechanical breakdown of
charged material occurs and fine-grained sludge consisting mainly of micron sized
glass pearls derives from the high temperature area around the raceway (Kallio 2011).
Lundgren et al. agree with the above presented formation mechanism of the BF off-gas
dust (Lundgren et al. 2011).

Amount, particle size distribution and composition of off-gas dust

The total amount of blast furnace dust and sludge removed by the gas cleaning system
are between 8 and 17 kg/t hot metal depending on how smoothly the blast furnace
operates (Oeters et al. 2009). Total Fe content in flue dust ranges 20?40 wt% and C
content 30-50 wt%. SiO2 , CaO, Al2 O3 , MgO and alkali oxides are present in lesser
contents. Characterization with XRD and LOM of flue dust has shown that Fe2 O3 is the
dominating iron oxide validating that Fe-containing particles originate from the top of
the BF or from the upper part of the shaft. Furthermore, C-containing particles in flue
dust have been confirmed to originate from coke at the top of the furnace but probably
also from lower parts of the shaft. (Lundgren et al. 2011, Leimalm et al. 2010)
Sinter-pellet operation has generated dust approximately 3.1-3.4 kg/tHM and sludge
3.0-5.1 kg/tHM at Raahe Steel Works (see Table 3). The amount of sludge rose from
4.0 kg/tHM to 5.3 kg/tHM while transition to full pellet operation. (Meriläinen 2012)
The EBF operation with 100% olivine pellet has shown flue dust 4.4-5.4 kg/t hot metal
(Sterneland & Jönsson 2003).
Figure 8 shows the particle size distribution of off-gas dust at Raahe Steel Works
in pellet-sinter operation and 100% pellet operation. The distribution has two clear
peaks. The first one indicates very fine micron-sized particles ended up to the sludge
and the latter peak indicates mechanically formed coarse particles separated in the dust
catcher. Separation of medium-sized particles goes overlapped between primary (dust)
and secondary (sludge) cleaning system.

27
Table 3. Amount of BF dust and sludge at Raahe Steel Works in pellet-sinter oper-
ation and full pellet operation (Meriläinen 2012).

Amount of dust or sludge (kg/tHM)

70% sinter / 30% pellet 100% pellet

BF1, dust 3.1 3.0

BF2, dust 3.4 5.1
BF1 & BF2, sludge 4.0 5.3

Fig 8. Calculated particle size distribution of off-gas dust (dust and sludge to-
gether) at Raahe Steel Works in pellet-sinter operation and 100% pellet operation
(Meriläinen 2012), modified.

The average chemical composition of Finnish blast furnace dust in sinter-pellet

operation and in full pellet operation is presented in Table 4. The largest difference
can be seen in C and Fe concentration. In full pellet operation the concentration of
carbon tends to increase and the concentration of Fe tends to decrease. (Meriläinen
2012) Kallio has also observed that the total iron content in flue dust in pellet operation
is significantly lesser than in combined sinter-pellet operation and the carbon content
vise versa which indicates that pellets are mechanically stronger and on the other hand
pellets cause more coke size degradation when charged to the furnace. Furthermore,
sinter with a more porous structure can bind itself more dust in the shaft. (Kallio 2011)
Furthermore, studies by Loo et al. show that sinter is more susceptible to degradation

28
than pellets under simulated blast furnace indirect reduction conditions. Fines generated
from pellets had minor size distribution than those of sinter (Loo & Bristow 1998b,a).

Table 4. Average chemical composition of dust collected from both blast furnaces
at Raahe Steel Works in sinter-pellet operation and in full pellet operation (Meriläi-
nen 2012).

Concentration (wt%)
70% sinter / 30% pellet 100% pellet
Component BF1 BF2 BF1 BF2

C 39.00 38.08 52.39 46.98

Na2 O 0.11 0.10 0.10 0.13
MgO 1.37 1.48 0.73 0.87
Al2 O3 2.02 1.99 2.31 2.19
SiO2 10.91 8.29 8.32 7.18
P 0.03 0.03 0.05 0.05
S 0.49 0.48 0.64 0.57
K2 O 0.13 0.11 0.20 0.27
CaO 3.58 3.51 7.68 6.41
Ti 0.19 0.20 0.19 0.19
V 0.076 0.074 0.16 0.15
Mn 0.16 0.16 0.22 0.22
Fe 27.02 30.19 16.35 21.45
Ni 0.016 0.017 0.009 0.011
Zn 0.033 0.032 0.053 0.062

Pellet screenings during the full scale test period with 100% pellet operation at
Ruukki Raahe Steel Works during 27.9.2010-18.11.2010 revealed that olivine pellets
had approximately 1.7% fines (<5 mm) after drying. When charging these pellets, fines
are released along ascending gases intensifying the off-gas dust generation. (Meriläinen
2012) These pellet fines are very fine as particle size (some tens of micrometers) and are
more likely to end up to the sludge depending on the extraction efficiency of the primary
cleaning system (Meriläinen 2012, Leimalm et al. 2010).
According to Kallio’s study of EBF off-gas dust samples, the total Fe content and
the C content in sludge is lesser than in flue dust. Furthermore, SiO2 , CaO, MgO, Al2 O3 ,

29
K2 O and Na2 O tend to concentrate on sludge instead of flue dust. (Kallio 2011) Ma et
al. point out that zinc is concentrated on the finest fraction in the off-gas dust. Thus,
zinc tends to concentrate on sludge instead of flue dust. (Ma et al. 2009) The same
observation has Kallio made in his study (Kallio 2011).

Factors affecting the off-gas dust formation

Lundgren et al. emphasize that off-gas temperatures and velocities together with an
even/uneven gas distribution have the greatest impact on the flue dust amount in off-gas.
Low off-gas temperatures, and thus lower off-gas velocities, are favorable for low flue
dust amounts. If fines accumulate in the shaft, ascending gases inside the blast furnace
tend to channel due to decreased permeability in the areas with increased amounts
of fines. Channeling in the burden leads to a circumstance in which coarser particles
ascend with the gases and thus enhances the generation of off-gas dust.(Biswas 1981,
Lundgren et al. 2010)
Sterneland and Jönsson have studied the effect of coating of LKAB olivine pellets
on dust formation with laboratory equipment and LKAB experimental blast furnace
(EBF). Testing of the coated pellets revealed that dust generation was significantly
decreased and sticking was prevented by the coating material when using coated pellets
in the blast furnace. Furthermore, gas utilization was higher for all tested coated pellets
indicating a better gas distribution preventing gas channeling. Olivine, quartzite and
dolomite were used as coating agents and bentonite as binder. The thickness of coating
was 0-0.1 mm. (Sterneland & Jönsson 2003)

2.2.3 Treatment and utilization of BF dust and sludge

Flue dust contains significant amounts of iron and carbon (see Table 4) and because of
this aim is to recycle as much as possible without disrupting the process. Additionally,
there is a realistic threat in near future that steel companies must pay landfill tax for
sludge dumped in the landfill site. This tax is 50 e/t from 2013 onwards but at this
moment there is no landfill tax for BF and LD sludge. Zinc, moisture and fine particles
are three principal barriers in recycling the blast furnace sludge. (Ma et al. 2009)
Generally, the flue dust is recycled through sinter making. At Ruukki Raahe Steel Works,
flue dust was recycled to the blast furnace process via the sintering plant until the end of
2011 when the sintering plant was shut down. In future, flue dust among other iron and

30
carbon bearing secondary raw materials will be produced to cold bonded briquettes and
charged as briquettes to the blast furnace. (Paananen et al. 2011) Flue dust can also be
agglomerated through pelletizing and utilized in iron making and steelmaking processes.
(Ma et al. 2009) The dried sludge from Ruukki Raahe blast furnaces is not recycled to
the process because of a high Zn concentration and is stored in an intermediate srorage.
(Meriläinen 2012)
The zinc content in blast furnace off-gas sludge is generally too high to be able to
recycle it to the blast furnace process, but too low to economically treat the sludge for
zinc through zinc recovery facilities. Additionally, high moisture content in sludge causes
extra difficulties in processing and economically utilizing the sludge. To overcome
the difficulties in managing the sludge problem, the simplest method is to reduce the
generation of sludge by making better the extraction efficiency of the primary blast
furnace gas cleaning system and to capture most of the off-gas dust as low-zinc dry flue
dust. with a dust cather of a cyclone (Ma et al. 2009)
A hydrocyclone is a general and efficient mechanical treatment method of blast
furnace off-gas sludge. The operational principle of the hydrocyclone is the same as the
dry cyclone’s but instead of gas the carrier fluid is liquid, in the blast furnace process
water. (Svarovsky 2000) According to a questionnaire study made by WorldSteel
Association, many steelworks that have invested in one or more hydrocyclones as
secondary off-gas cleaning equipment have managed to improve the utilization rate of
sludge significantly. Only four respondents of 26 announced to dump all the sludge to
the landfill site as 11 respondents recycled 100% sludge. According to the study, 83% of
blast furnace sludge was utilized at the steelworks. (WorldSteelAssociation 2010)
Other technical solutions to separate zinc from ironmaking and steelmaking dusts or
sludges are discussed more precisely in the section of BOF slag and dust.

2.3 CO2 Emissions from Blast Furnace Ironmaking

2.3.1 The present state

The Steel industry has been aware of the climate change threat since the late 1980s and
has proposed solutions early. In many developed countries, such as Japan, South-Korea
and European countries, steel producers have managed to reduce their CO2 more than
in any other industrial field (50-60% reduction in CO2 emissions). Meanwhile the
worldwide production of steel has grown and much of the growth has occurred in

31
countries with inferior technological development. Worldwide anthropogenic emissions
of CO2 in 2004 amounted to 49 Gt of which the industrial sector represents 19.4% and
the steel industry 4-7% depending on sources. Therefore, the steel industry amounts
from one fourth to one third of the entire CO2 emissions from all industrial sectors.
(Birat et al. 2008)
The reason steel production produces a large amount of CO2 is due to two reasons:
high consumption of energy factory wide and high carbon requirement to act as reducing
agent of iron ores. The cheapest fuel that fulfills this purpose is carbon in the form
of coke and coal. The fuel rate of a conventional blast furnace is slightly above 500
kg/ton hot metal, most of which consists of coke. Coke rate can be decreased by partial
substitution with other (hydro)carbon sources, such as pulverized coal, natural gas,
oil or recently plastic wastes and charcoal. Injection of pulverized coal is already a
well-established technology. Coke cannot be entirely replaced by injected fuels due to
physical restrictions: it is the only solid material below the cohesive zone and serves to
support the above material column and preserve of good permeability of the burden.
Blast furnace and coking oven gases are consumed in many of steel factory’s
processes as a source of energy. Ironmaking processes account for roughly 70% of the
CO2 emissions in steel production. The CO2 emissions produced by various ironmaking
processes are divided as follows: 28.8% blast furnace gas, 18.4% coke oven, 33.2%
hot stove and 19.6% sintering machine. Even though not all of the processes actually
produce gas, they can be considered sources of CO2 due to their requirement of energy.
(Ariyama et al. 2005)
In order to fulfill the Kyoto protocol requirements, the European Union has in-
troduced Emission Trading Scheme (EU ETS). It expects steel industry to operate
existing processes more efficiently and more environmentally. (Ghanbari et al. 2011) If
companies do not have the sufficient allowances, they can either implement measures to
reduce their own emissions or to buy emission allowances. The rise of CO2 emission
costs is a strong incentive for European companies to further develop their processes.
There is an abundance of research related to blast furnace technology and CO2
reduction. Due to this reason some concepts had to left out of this review due to limited
time resources. Also, some technologies, such as CO2 stripping from blast furnace top
gas and it’s storing or use for methanol synthesis were considered to be out of the scope
of this review. It should be noted that capture and storage of top gas CO2 is mandatory
for the economy of many processes under development such as top gas recycling.

32
Optimization of energy in the blast furnace

Any process that consumes or loses energy in the blast furnace also increases fuel rate
and therefore CO2 emissions. There are many factors that affect the total consumption of
energy. Heat losses compose a significant portion of blast furnace energy consumption.
Heat losses occur through the lining and with top gas, slag and hot metal. One of the
ways to decrease heat losses through the lining is to control gas flow in the furnace.
High central flow of gases is preferred for lower heat losses. The decrease of shaft
temperature is another possible method to reduce heat losses through the lining. The
shaft temperature can be decreased by using highly reactive coke. This method is under
current research, however, it is not entirely without negative effects. Lower thermal
reserve zone temperature is also expected to improve gas utilization. Sensible top gas
temperature as well as slag and hot metal temperature are also means of optimizing
energy consumption.
Blast air is blown in through the tuyeres along with injected fuels. Blast temperature
has been raised in the past. In modern blast furnaces the blast temperature generally
varies between 1100 and 1200 ◦ C. One of the benefits of higher blast temperature is the
increase of input energy, which in term reduces reducing agent rate. In many cases,
however, we are approaching the limits of blast temperature. Economical, process and
hardware are some of the reasons that limit the blast temperature. Ribbenhed et al.
(2008) reported that at SSAB a raise of blast temperature by 100 ◦ C in 2005 achieved
a 10 kg/thm reduction in reducing agent rate. Further increase of blast temperature
would require investment of new hot stoves. Other factors, such as moisture of input raw
materials, also affect the total energy consumption. For example dry quenching of coke
(with nitrogen instead of water) has been applied to reduce the fuel rate.

Increase of injected fuels

In the past years there has been a major emphasis on increasing the amount of fuels
injected to the blast furnace through the tuyeres. The purpose of injectant fuels is to
reduce the consumption of coke. Globally the most common injectant fuel is pulverized
coal. Natural gas is also used in countries with easy access to it. In Finnish blast
furnaces, residual fuel oil is currently used as the injectant fuel. One of the benefits of
injectant fuels is their lower CO2 rate compared to coke. For example pulverized coal
actually raises the reducing agent rate (RAR) because the coke replacement rate is less

33
than 1.0, but reduces the total amount of carbon consumption due to higher input of
hydrogen compared to coke. For natural gas and residual fuel oil, the proportion of
hydrogen is even greater. The increase of injected fuels has been one of the primary
methods to reduce CO2 emissions and based on the amount of recent research it will
remain important focus in the near future.

2.3.2 Future technology

In the past, large reductions in total carbon consumption, and therefore CO2 reductions
have been achieved. However, the current method of blast furnace production and
carbon consumption are approaching theoretical limits. It has been calculated that
reductant rate of today’s optimized blast furnaces is only 5% above the theoretical limit
of an ”ideal” blast furnace. Individual blast furnaces can still achieve CO2 reductions
by enhancing operation, but large CO2 reductions in well optimized blast furnaces
will require implementation of new technologies. (Hanrot et al. 2009) Some of the
technologies and methods described in this chapter are already in small scale industrial
use, but so far lack large scale industrial utilization.

Low reducing agent rate operation

In order to reduce CO2 emissions, the primary goal is to achieve low RAR operation.
The word RAR relates to reducing agent rate, meaning the amount of carbon based
fuel spent on reducing a certain amount of iron ore. Some of the ways to reduce RAR
are: the reduction of heat required for reducing (charging of scrap, pre-reduced ore),
lowering heat losses (lowering the thermal reserve zone temperature, control of gas flow),
promotion of hydrogen reduction (use of waste plastics, natural gas or another hydrogen
rich fuel), the injection of reducing gas (for example recycled top gas), increase of heat
input (increase of blast temperature, decrease of moisture), decrease of sensible heat of
slag and metal. (Ariyama et al. 2005)
In order to reduce CO2 emissions in, it is important to analyze the steel plant as a
whole, not just the blast furnace process alone. Many of the steel factory’s processes are
interconnected and dependent on energy produced from blast furnace or coke oven
gas. Energy consumption in other processes coking ovens, sintering lines or hot stoves
are also sources of CO2 emissions. Improvement in the heat balance of any of these
processes results in the reduction of factory wide CO2 emissions. If the blast furnace

34
would operate with low RAR without factory wide decrease in energy consumption, the
other processes would have to be operated with purchased energy negating the CO2
benefits. Therefore, the first objective is to reduce energy consumption in all individual
steelmaking processes. Then the focus should be on low RAR production in the blast
furnace while continuing to produce adequate energy for the downstream processes.
(Ariyama et al. 2005)
It should be noted that the benefits of low RAR operation are strongly tied to the
price of energy. For example in Japan in the past steel factories have been dependent on
energy from blast furnace gas and have instead strived for high RAR operation due
to high price of Japanese energy. The focus, however, is shifting toward low RAR
operation. One of the reasons for this is the increased price of coking coal. (Ariyama
et al. 2005)
Low RAR-operation places significant challenges on raw material properties,
especially coke. Increase of injected fuels results in decreased descending speed of
coke in the blast furnace, which means increased time under mechanical, thermal and
chemical stresses. Sufficient strength of coke is of primary importance for the sake of
good blast furnace operation. It has been observed that weak coke degrades in the lower
parts of a blast furnace and impairs permeability of the burden. Low permeability in the
dead man increases peripheral gas flow and heat-loss in the lower part. Burden descent
could also become unstable and slag flooding occur in the lower part. These problems
must be solved in order to achieve low RAR operation. (Ariyama et al. 2005)

Use of pre-reduced iron ore

Manufacture of pre-reduced ore and its utilization in blast furnaces is considered one
of the more promising technologies related to decrease in CO2 emissions. With the
use of pre-reduced ore it is possible to decrease the reducing agent rate and thereby
save energy. Lower grade ores that are unsuitable for sintering can also be utilized in
pre-reduction. It is important to include the energy, and therefore produced CO2 , used in
pre-reduction process in the calculations. Pre-reduction can be achieved using natural
gas or another suitable energy source with lower carbon content. It can take place in a
country with access to natural gas and the pre-reduced ore can then be transported to
foreign countries. (Kunimoto et al. 2006)
In order to achieve high productivity, the degree of ore pre-reduction is limited to a
degree where there is no visible decline in the reduction rate. According to calculation,

35
time required for 90% reduction at 880 ◦ C is 120 minutes, whereas 60% reduction can
be achieved in about 20 minutes in the same temperature. The productivity with the
latter degree of reduction is roughly six times higher. By taking into account production
and transportation to Japan, it was calculated that 60% pre-reduction could decrease
total energy consumption by 0.3% and total carbon consumption by 2%. (Kunimoto
et al. 2006)
Charging of metal scrap in the blast furnace is also an option, although it is not
entirely economical. Wang et al. (2009) proposed a model for the optimization of
BF-BOF process where metal scrap was charged in both processes.

Top gas recycling

The blast furnace top gas consists of roughly 25% of CO2 and CO, usually less than 10%
H2 and H2 O combined while N2 accounts for the rest. In top gas recycling scenarios,
normal blast gas is partially replaced by top gas which has been filtered and heated to
blast temperature. Top gas recycling has been through industrial trials, but is still under
development for large scale use. The recycling of top gas would be beneficial due to
optimal utilization of reducing components CO and H2 .This would mean that less or no
blast furnace gas would be available for energy production. However, the energy by the
steel factory could be produced with other methods that do not produce CO2 emissions.
Generally the shaft efficiency would increase due to higher reducing potential and/or
increased temperature.
Top gas recycling has been studied with mathematical analyses. The simple recycling
of normal blast furnace top gas would decrease productivity and increase fuel rate.
Metal and raceway temperature are rapidly decreased with CO2 injection due to its
highly endothermic reaction with coke. It is estimated that no more than 20% of top gas
can be recycled by the simple method. The use of increased oxygen enrichment of blast
would decrease the severity, but still also produce negative results. The optimal method
is to use hot reducing gas stripped of CO2 . It was predicted that about 25% increase in
production can be achieved simultaneously with a 20% reduction in fuel rate by using
CO2 stripped top gas. With CO2 stripped gas it may be possible to stably operate the
furnace at 100% gas recycling. (Austin et al. 1998)
The possibilities of injecting recycled top gas are: directly into the shaft area,
through the tuyeres, or both shaft and tuyeres. In the case of shaft injection, the
furnace temperature shows remarkable increase, whereas with tuyere injection the shaft

36
temperature is decreased. A computational model predicted a 2.1, 11.4 and 15.7%
increase in productivity and 3.3, 15.3 and 18.3% decrease in reducing agent rate for
shaft, tuyere and both shaft and tuyere injection. Therefore the most optimal method is
to inject recycled top gas both at the shaft and at the tuyeres. (Chu & Yagi 2010)
It has been calculated that optimal degree of top gas recycling varies considerably
with the costs of CO2 emissions. With low costs of emissions the traditional blast
furnace method was the most economical, but with high CO2 costs the top gas recycling
became more economical. Also, with a high degree of top gas recycling it is more
economical to heat the recycled gas instead of the oxygen blast. (Helle & Saxén 2011)
Recycling of decarbonated top gas may cut CO2 emissions by nearly 30% according
to calculations (Babich et al. 2010). In 2007 in an EBF (experimental blast furnace)
campaign in Sweden stable operation was achieved with decarbonized top gas recycling
during a 2-week operation. Carbon savings of up to 24% were exhibited. It was
concluded that this method could allow 65% reduction of CO2 emissions in the whole
steel mill if CO2 storage was in place. The industrial trials will be scaled up in the next
phase of the ULCOS project. (Birat 2009)

Charcoal

The use of charcoal is linked to small blast furnaces in Brazil, where it has been used
in for a long time period of time as an injectant fuel (replacing pulverized coal). Due
to the urge to reduce CO2 emissions the utilization of charcoal in larger scale blast
furnaces has became a point of interest. The research on its use for larger furnaces is
still limited to mathematical and small-scale laboratory modeling. The use of charcoal
or other bio-mass is favorable because all the carbon in charcoal is generated from
CO2 of the atmosphere. Therefore it can be considered CO2 neutral. Charcoal also has
other advantages, such as higher expected productivity and lower contents of harmful
components. (Babich et al. 2010)
According to calculations made for the ULCOS project, the replacement of pul-
verized coal with low ash and high basicity charcoals could decrease blast volume,
slag volume and therefore enable operation with lower coke rate. Furthermore, heat
losses are expected to decrease and furnace productivity to rise. Considering charcoal as
CO2 neutral, CO2 output is calculated to decrease 44.8, 41.6 or 36.8% depending on
charcoal grade when replacing pulverized coal 100% with charcoal. The surface area of
charcoal is 60-350 greater compared to pulverized coal. For some charcoal grades the

37
combustion properties have been observed to be similar to pulverized coal, for other
grades they are much better. Its CO2 reactivity is also higher compared to pulverized
coal, thereby unburned charcoal is expected to be more easily consumed outside the
raceway. Charcoal chemistry is highly dependent on production conditions but not on
the wood type. (Babich et al. 2010)
The behavior of charcoal outside the raceway is of primary importance. Unburned
fines can seriously impair blast furnace permeability, cause dirtying of the deadman and
finally reduce productivity and increase coke rate. In addition to being CO2 neutral,
charcoal has another advantage: its reactivity is higher compared to coke, which makes
it possible to lower the thermal reserve zone temperature of a blast furnace. The
incorporation of charcoal into the coking mix can decrease the threshold temperature of
the Boudouard reaction by 100◦ C to 200◦ C. (Hanrot et al. 2009)
By charging only 20 kg/THM charcoal together with coke, the reserve temperature
would drop down to charcoal gasification threshold temperature. Due to high reactivity,
that charcoal would be consumed in the upper part of the blast furnace without producing
fines and decreasing permeability. It is calculated that this would produce saving of 30
kg/thm coke. (Hanrot et al. 2009) It should be noted that there are other sources of
biomass that could possibly be utilized in blast furnaces, such as bio-oil or syngas (bio
gas), though they are considered to be better suited for other purposes. (Birat 2009)

Waste plastics

The use of waste plastics as an alternative fuel in a blast furnace can reduce CO2 due
to its higher hydrogen content compared to coke or pulverized coal. In many cases
waste plastics are simply incinerated at the present moment. For example in Japan only
39% of waste plastics are utilized for recycling. The use of waste plastics has already
been commercialized in some blast furnaces in Germany and Japan. Polyvinyl chloride
is considered unsuitable for blast furnace use due to formation of hydrogen chloride,
which could cause corrosion of blast furnace facilities. (Asanuma et al. 2000)
The injection of waste plastics into a commercial blast furnace has been studied in
Japan. High-speed cameras placed in the tuyere and gas sampling revealed different
combustion of plastics compared to pulverized coal. Fine size range plastics combusted
instantaneously similar to pulverized coal, but higher size range plastics indicated
slower combustion. Based on observations it was clear that combustion of plastics is
inferior to pulverized coal. Agglomerated plastics proved better combustion compared

38
to crushed plastic despite similar size range. Despite slower combustion, on the contrary
to pulverized coal, higher size range plastics showed better overall degree of combustion
in a raceway hot model. It was thought that smaller size range plastics are quickly blown
away from the raceway, whereas higher size range plastics rotate in the raceway for a
longer period of time. The CO2 reactivity of plastics was 10 times higher compared
to pulverized coal indicating efficient consumption of unburned plastics in the blast
furnace. It was estimated that limit of waste plastics injection could be between 140 and
250 kg/thm. (Asanuma et al. 2000)
The addition of waste plastics into the coking coal mix has also been under recent
study. The amount of possible plastic addition, however, is thought to be quite small
without impairment of coke quality. Incorporation of 2 wt% plastics in cokemaking can
achieve 2% CO2 mitigation. The use of plastics for syngas production and injection at
the tuyeres can proved a much larger reduction (7%). (Hanrot et al. 2009)

Natural gas

Natural gas is used as an injectant fuel in countries where its price is competitive with
pulverized coal. It accounts for 5% of the world steel production today. It is the leanest
in CO2 today due to the replacement of carbon by hydrogen in the form of CH4 . For
example SSAB in Sweden has planned to switch from pulverized coal injection to
natural gas injection depending on the availability of natural gas in Sweden. This switch
is estimated to cut CO2 emissions by 8%. (Ribbenhed et al. 2008)

2.3.3 Efforts to reduce blast furnace CO2

Besides larger projects described below, there are also efforts by individual countries to
reduce CO2 emissions. For example Japan has set a target of 10.5% reduction in CO2
emissions under a Voluntary Action Plan (Ariyama et al. 2005).

ULCOS

The ULCOS-program is a joint operation of European steel manufacturers and research

institutes to achieve significant reduction of CO2 emissions in the near future. ULCOS
started in 2004 and includes 48 organizations in 15 European countries and is likely the
largest endeavor to reduce CO2 emissions among all industrial sectors (Birat 2009).

39
It examines an extremely wide spectrum of innovative technologies including the
following: improvements in BF operation with top gas recycling into the blast furnace;
the use of non-carbon reducing agents (hydrogen, electricity, natural gas); the use of
sustainable biomass; CO2 capture and storage. The schedule for industrial application
however is at least 10 to 20 years. The ambition of ULCOS is to reach 50% reduction in
CO2 emissions. (Hanrot et al. 2009)
In the first phase of ULCOS seventy different process routes were investigated.
Some of the more promising options have been chosen for further study and small scale
trials. In the future the most promising methods will be subjected to full scale industrial
trials. It has been concluded that ULCOS process routes are not yet competitive with the
baseline blast furnace route. In the long term, however, when the cost of carbon based
fuels increases, they all, more or less, become competitive, some as early as in 2015.
(Birat 2009)

SHOCOM

SHOCOM is another project aiming to reduce CO2 emissions. It has received support
from the European Commission. Compared to ULCOS, SHOCOM project looks at less
ambitious targets compared ULCOS (10% cut in CO2 ), but at application in the short
term. The options proposed in SHOCOM are based on two ideas: 1) the lowering of
thermal reserve zone temperature in order to decrease the need for carbon; 2) the use of
two alternative fuels: renewable charcoal and waste plastics. (Hanrot et al. 2009)

2.3.4 Challenges related CO2 reduction

Countries around the World have agreed that reducing the production of greenhouse
gases is of primary importance to contain global warming. However, mainly due to
economic reasons, many steel companies are unwilling to make changes to reduce their
own emissions. Firstly, the application and development of new blast furnace technology
requires large financial investments. Secondly, the current method of blast furnace
production is considered the most cost effective way. Without significant financial
incentives, the application of CO2 reducing technology would raise the cost of producing
iron. Steel companies are unwilling to reduce their emissions as long as it doesn’t meet
their financial interests. Not all of the future technology will, however, raise the price of
production. Some developments are expected to both increase productivity and reduce

40
CO2 emissions.
The primary way to reward reductions in CO2 is the use of financial incentives.
Europe is the forerunner in this field with its emission trading scheme. The lack of
incentives, however, is a significant problem in most parts of the World. For example,
China already produces 51% of the CO2 emissions of the worldwide steel industry
(Huang et al. 2010). Without worldwide incentives the companies that are punished for
their CO2 emissions would have a significant disadvantage when competing against
companies without emission penalties. This could lead to a larger part of steel production
being moved to countries with less developed technology.
In the blast furnace field, there is also a habit of playing it safe. Iron producers are
unwilling to make changes to their processes in fear of a catastrophe and would rather
settle for the old safe method of production. It is hard to have new ideas or technology
applied in the ironmaking industry.

41
42
3 Environmental aspects of EAF slag, dust
and off-gas
Authors: Matti Aula and Juha Roininen

3.1 Introduction

Electric arc furnace (EAF) is the dominant way of producing steel from the metal scrap.
In 2010 28% of the total crude steel production was produced with electric arc furnaces
(Bureau Of International Recycling 2012). The main difference between making steel
from scrap and ore is that the scrap is already in metallic form and reducing agents are
not needed in as great amounts as with ore. The scrap still has to be melted, which is
done with electricity in EAF. The usage of electricity is usually somewhat lowered by
usage of oxygen blowing which burns the carbon in steel bath and provides chemical
energy. (Birat et al. 1999)

3.2 EAF slag practice

The electric arc furnace (EAF) operates as a batch melting process. Every processed
batch has unique steel and slag composition. Main variations come from added raw
materials and for that reason every heat is needed to be operated with consideration
of many variables. As every heat is aimed for certain final composition for steel, that
difference can be seen also from slag produced with EAF processing. The slag produced
from EAF is containing a mixture of oxides consisting mainly of calcium, iron and
silicon oxides. As a minor constituent, there is some magnesium oxide preferred to
be added for proper influence with refractory used in furnace. Also from scrap some
aluminum, chromium and manganese oxides are present even that those are not desired
in melt or not needed to be aimed for slag phase (Väinölä & Kumpulainen 2011, Kwong
& Bennett 2001, Jones 2012). Figure 9 shows the main equipments for the process.
The following three tables show the typical constituents of an EAF slag and many
variations in the slag. These variations are related to many processing procedures in the
electric arc furnace. After processing in EAF, big difference for steel quality is done by
versatile ladle metallurgical treatments in order to achieve aimed level of final product.

43
Fig 9. Main equipments for the electric arc furnace (Jones 2012)
Slag from EAF at this moment is needed to be taken away with consideration that slag
from the process is not preferred to go into the next phase in processing at the melt shop
level (Väinölä et al. 1995, Väinölä & Kumpulainen 2011).

44
Table 5. Slag variation for Ovako Steel Ab in Hofors (Lindström 2004)

1 2 3 4 5 6 7 8 9 10

MgO 3.64 5.19 3.78 4.56 3.84 4.09 5.51 2.74 4.93 3.67

CaO 37.6 40.6 37.5 38.9 44.2 41.9 41.5 42.5 46.4 41.0

Cr2 O3 3.30 2.66 2.69 2.45 2.30 2.33 2.60 1.96 2.25 3.05

MnO 5.54 5.47 6.04 4.72 4.88 4.06 3.75 6.04 5.10 4.59

FeO 9.36 7.46 7.87 4.2 8.74 9.66 10.9 6.24 6.35 14.0

Fe2 O3 17.1 13.6 17.5 20.3 12.8 4.69 5.64 18.7 9.61 4.07

Femet 3.73 2.45 4.85 4.36 4.78 6.68 7.11 5.13 3.08 9.61

Al2 O3 6.19 7.95 6.78 8.64 5.73 7.31 6.89 4.54 7.37 9.50

SiO2 12.0 13.3 9.81 11.0 11.3 13.5 14.8 9.20 12.4 12.0

C 0.30 0.052 0.74 0.72 0.98 0.88 0.17 0.51 0.38 0.79

S 0.14 0.15 0.16 0.24 0.19 0.19 0.16 0.18 0.17 0.18

Sp-fakt. 5.26 7.66 6.19 8.33 5.38 6.96 6.69 4.11 7.23 8.71

B2 3.13 3.05 3.83 3.54 3.91 3.10 2.80 4.61 3.74 3.42

Table 6. Slag variation sources and composition range for main oxide materials
(Jones 2012)

Component Source Compostition range

CaO Charged 40-60%

SiO2 Oxidation product 5 - 15 %
FeO Oxidation product 10 - 30 %
MgO Charged as dolomite 3-8%
CaF2 Charged - slag fluidizer
MnO Oxidation product 2-5%
S Absorbed from steel
P Oxidation product

45
Table 7. oxide materials is average values for analyzed slag compositions from
Ovako Steel Oy Ab Imatra. (Väinölä & Kumpulainen 2011)

% %

Na2 O 0.20 Cr 1.38

MgO 5.01 Mn 3.83
Al2 O3 5.03 Fe 18.17
SiO2 12.18 Ni 0.01
P 0.21 Cu 0.01
S 0.11 Zn 0.03
K2 O -0.01 Sr 0.06
CaO 42.59 Zr 0.00
Ti 0.30 Ba 0.04
V 0.10
3.2.1 Slag in different processing periods

The electric arc furnace is operated with several heats during one day and these heats are
coming in cycles, which are planned to contain similar heats. And one heat is made up
of the following main operation stages (Jones 2012):

– Furnace charging
– Melting
– Refining
– De-slagging
– Tapping
– Furnace turn-around

Needed materials are fed in to the process with buckets in the charging stage of
the operation. These buckets may contain also lime and feldspar for the aimed fast
reactions with the materials that become oxidized already during the melting period.
Best results are achieved if all slag formers are not needed to be fed during the charging.
If operation systems have equipment for lime injection behind the electrodes good
results are achieved for additions and operation effectiveness overall. (Jones 2012,
Väinölä & Kumpulainen 2011)
Also some part of the slag formers can be in the form of old refractory materials
taken from demolished linings. This material is crushed in such size range, that those

46
can be fed in certain limited amounts into the process and those are molten during the
time of one heat. To help fast melting in to the slag, this material is mostly in form of
magnesia containing refractory, so that material itself is helping to lower the melting
point of the lime, which is the fraction in slag with high temperature melting point.
(Kwong & Bennett 2001, Väinölä & Kumpulainen 2011)
During the heating operation several metallic components are forming new oxide
components into the slag phase. Some of these are needed to be going into the slag,
to make sure that final steel composition is desired. All of these reactions are also
making part of the needed energy in form of additional chemical energy. To make these
reactions even more effective some part of the oxygen is blown with the lance operation
period. The oxygen reacts with several components in thermodynamic order and after
nothing else is available, iron will react to form a component to lower even more solidus
temperature of the slag phase. This lance operation is normally done in refining period,
but also some cases during the melting period. With this period also some carbon is
burning near the electrodes, where is already enough high temperatures for carbon to be
the most active component (Jones 2012)
Operation of the furnace in the refining stage is most interesting for slag chemistry
and from metallurgical operation point of view. At this moment all material is already
molten as been presented in Figure 10.

Fig 10. The refining period of the EAF melt processing for the carbon steel making.
(Engström 2007)

47
 Many times scrap and other raw materials are containing such a large amounts
impurity elements, which are advantageous to remove into the slag as early in the
processing of the heat as possible. For ex. phosphorous removal is more effective while
the bath temperature is still low. The furnace can many times be tilted backwards and
slag can be poured out of the furnace through the slag door. That way this removal of the
slag before heating up material into the tapping temperature eliminates the possibility of
phosphorus reversion. (Jones 2012, Väinölä & Kumpulainen 2011)

P + O + CaO → CaO · P2 O5 (1)

De-slagging operation is carried out so that can be sure that for steel unwanted
impurities are removed from the furnace and not going into the next ladle operations. In
to the slag phase many of the undesirable elements (chromium, phosphorous, sulfur
etc.) are oxidized and enter in slag phase. (Jones 2012, Väinölä et al. 1995, Väinölä &
Kumpulainen 2011)

3.2.2 About phosphorous and sulfur removal

All of the refining reactions are dependent on the availability of oxygen. Oxygen via
lance operations are aimed on desired level for carbon and with that aim many of those
compounds, which can be analyzed in larger amounts from slag phase, have higher
affinity for oxygen than with the carbon. And these elements in these process conditions
are heading to be part of the slag phase, when these compounds normally are much less
dense than those compounds inside metal phase.
Phosphorus and sulfur occur normally in the furnace charge in higher concentrations
than are generally permitted in steel and these must be removed. As has been well known
these two elements can’t be removed in similar conditions. To remove phosphorus slag
basicity, temperature and highly oxidizing conditions are favorable. FeO level is good
indicator for enough good oxidizing conditions. If needed to do sulfur removal higher
temperature is needed and also oxygen level is needed to be much lower. For that reason
only some part of the sulfur removal is done in EAF processing with the help of the
high basicity, which will be favorable for both elements removal from steel phase. Still
some reason is needed because over saturating with lime can lead to an increase in slag
viscosity. Too high slag viscosity will lead trouble with slag reactivity and slag foaming
benefits can’t be realized for processing.
Phosphorus containing slag is needed to be taken away if very low level is needed

48
Table 8. Refining with oxygen will provide several reactions inside operation unit
as it will also provide chemical energy (Pfeifer et al. 2005)

Chemical reactions in the steel melt Reaction enthalpy

Si + O2 → SiO2 -8.94 kWh/kgSi -11.20 kWh/m3 O2

Mn + 0.5 O2 → MnO -1.93 kWh/kgMn -9.48 kWh/m3 O2

2 Cr + 1.5 O2 → Cr2 O3 -3.05 kWh/kgCr -9.42 kWh/m3 O2

2 Fe + 1.5 O2 → Fe2 O3 -2.05 kWh/kgFe -6.80 kWh/m3 O2

Fe + 0.5 O2 → FeO -1.32 kWh/kgFe -6.58 kWh/m3 O2

C + 0.5 O2 → CO -2.55 kWh/kgC -2.73 kWh/m3 O2

2 Al + 1.5 O2 → Al2 O3 -5.92 kWh/kgAl -13.84 kWh/m3 O2

Mo + O2 → MoO2 -1.70 kWh/kgMo -7.92 kWh/m3 O2

S + O2 → SO2 -2.75 kWh/kgS -3.94 kWh/m3 O2

2P + 2.5 O2 → P2 O5 -5.54 kWh/kgP -8.58 kWh/m3 O2

Chemical reactions in the gas phase Reaction enthalpy

C + O2 → CO2 -9.10 kWh/kgC -4.88 kWh/m3 O2

CO + 0.5O2 → CO2 -7.01 kWh/m3 O2

H2 + 0.5O2 → H2 O -5.99 kWh/m3 O2

and temperature is needed to be raised high. Usually the phosphorus is reduced by 20 to
50% in the EAF. Especially when aimed low carbon level less than 0,1%, it is possible
in phosphorous aim to lower than 0,01% level. (Jones 2012, Väinölä & Kumpulainen
2011).
Sometimes fluorspar is added to help lower the viscosity of the slag, this is needed if
not iron oxide and other fluxes are not enough to reach desired level of viscosity. Also
many places process is provided with the bath stirring possibility with inert gas. This
is also beneficial because it renews the slag/metal interface as a consequence it will
improve the reaction kinetics Jones (2012).
For sulfur removal optimal conditions are mostly after or during tapping in at the
ladle operations. Some part is removed even that oxidation level of the bath is high.
Partly this sulfur is dependent on slag chemistry.

49
3.2.3 Slag foaming in EAF processing

One of the most important reactions during EAF operation is to have slag foaming
happening inside process unit. Carbon is injected into the slag, where it will reduce
earlier oxidized FeO back to the metallic iron or other major possible reactant could be
same time injected oxygen. These reactions will provide enough carbon monoxide
inside, which can make foaming slag reality for the benefit of the processing economy.
Other relevant phenomenon to make slag foaming more easily to occur and last long
time in stabile condition is to have chemical composition correct, temperature certain
level and especially slag physical- and chemical properties to be such that viscosity,
surface tension, basicity, solid particles and active components on surface tension are
beneficial for slag foaming. During slag foaming, slag may overflow the tapping level in
the EAF and flow out of the slag door as can be seen from Figure 11. (Luz et al. 2011)

Fig 11. Refining and slag foaming with carbon- and oxygen lance operation
Väinölä & Kumpulainen (2011)

The electric arc has extremely high temperature and from that point of view it is
obvious that the good isolation of the arc by slag foam plays a key role in process
efficiency. As can be seen from Figure 12 several energy efficiency related considerations

50
on slag is needed to be controlled in EAF processing. When only half of the electric arc
length is covered in slag layer, it will result that two thirds of the total energy could be
transferred from the arc into the liquid metal and one third will be lost. However, if the
arc is totally immersed into the slag, energy usage will increase from 65 to 93 %. At the
same time also refractory consumption, equipment maintenance and overall economy
will benefit from controlled slag foaming.

Fig 12. Electric arc furnace energy efficiency vs. slag foaming benefits (Ameling
1986)

Aim to produce CO gas is important, because it offers a less expensive form of

energy. In EAF operations aim is to lower carbon very low level, but high temperature,
cheaper energy, to get better metal yield and slag foaming create combination, where
is economical inject oxygen with carbon into the process. That amount can supply
between 30 and 40 % of the net heat input to the furnace. Evolution of carbon monoxide
is very important for slag foaming. Coupled with a basic slag, CO bubbles are tapped in
the slag causing it to ”foam” and helping to bury the arc. This gives greatly improved
thermal efficiency and allows the furnace to operate at high arc voltages even after a flat
bath has been achieved. Injection is needed to be performed in just under slag/metal
interface. This placement should be found to be exact, because with small difference in
placement can result be strong in slag foaming operation. (Halmeenpää 2011)

51
3.2.4 Tapping of the process

Before tapping and during slag foaming a lot of slag material is taken out from slag door.
When tapping is started tap-hole is opened, and the furnace is tilted and steel starts to
pour into the ladle. Several metallurgical operations can be done during this time, but
need is to see that operator has correct tools to prevent slag going further processing and
make ladle operations more difficult (Väinölä et al. 1995).

Fig 13. To control correct amount slag in ladle new equipment is needed (Väinölä
& Kumpulainen 2011)

3.2.5 Utilization of the slag from EAF processing

Using of slag and processing, after use in metallurgical process, has always differences
between places of production. Mainly what needs to be taken care is enough spinel
forming slag formers and enough high cooling speed for material. Mainly metals in
slag are not that valuable, so that big scale processing would be needed. Mainly lot of
effort is concentrated on crushing and sieving so that correct size material is produced.
Most of the metals are taken with magnets and returned back in to melting. Because

52
material is containing porosity and it has certain edged surface overall, material have
several excellent properties for earth construction. In Finland thermal insulation and
load carrying capacity combination for material, means secure market for utilization in
road construction purposes. In other countries material is widely used in asphalt layer of
the road.

Fig 14. To control leaching slag is taken already hot away from melt shop and
cooled down in thin layer with help of water (Väinölä & Kumpulainen 2011).

3.3 Environmental aspects of electric arc furnace dust

Nearly every modern electric arc furnace (EAF) is equipped with gas collection and
cleaning system. The gas sucked out of the EAF is called off-gas and it contains certain
amount of solid dusts. The purpose of the system is to improve working conditions near
the EAF and to minimize generation and emission of toxic gasses. The most common
way to gather off-gas and dust is to use direct evacuation system, in which the gas is
sucked out of the furnace through a hole on the furnace roof and taken to baghouse,
where off-gas and EAF dust is separated. (Jones et al. 1998)

53
3.3.1 Characteristics of EAF dust

The amount of dust generated in EAF is quite significant, about 1 - 2 % of the weight of
the furnace charge. Compositions of EAF dust vary depending on the type of scrap
used in EAF (López & López-Delgado 2002). Table 9 shows example of EAF dust
composition.

Table 9. Example of EAF dust composition (Lee & Song 2007).

ZnO Fe2 O3 PbO CuO CdO Al2 O3 CaO MgO Na2 O K2 O Cl

27.39 32.46 4.48 0.31 0.07 1.27 3.23 2.69 3.11 5.23 5.95

High amount of ZnO and Fe2 O3 seen in Table 9 is typical for EAF dust. Other
noteworthy components are hazardous heavy metal oxides PbO and CdO. (Liebman
2000) EAF dusts are considered hazardous wastes in most industrialized countries due
to leachability of these elements (López & López-Delgado 2002). High amount of ZnO,
PbO, CdO and alkali oxides is result of subsequent vaporization and oxidation (Ma &
Garbers-Craig 2006).
Guézzennec et al (2005) distinguished two major categories of particles in the dust,
large particles size from dozen to a few thousand micrometers and finer particles with
lower than 20 µm. Major part of the dust falls to the finer particles category and are
spherical in shape. These particles are result of CO bubble bursting, which is explained
in the following chapter. (Guézennec et al. 2005)

3.3.2 Dust generation

Dust formation in electric arc furnace can be divided to 5 different categories according
to Figure 15.
The dust generation mechanisms and their corresponding numbers in Figure 15 are
as follows: volatilization (1), projection of droplets at the impact points of the arc or of
the oxygen jet on the steel bath (2), projection of fine droplets by bursting of CO bubbles
coming from the steel bath (3), bursting of droplets within an oxidizing atmosphere
(4) and direct fly-off of particles (5). (Guézennec at al 2005) According to different
studies (Guézennec et al. 2005, Ma & Garbers-Craig 2006) the main dust generation
mechanisms are bursting of CO bubbles near arc (2) and on slag surface (3), which

54
Fig 15. Dust generation mechanisms in EAF. (Guézennec et al. 2005).
generates approximately 60 % of the total EAF dust emissions and volatilization, which
generates 27 % of total EAF dust. Incorrect charging of lime can also result in steep
increase in direct fly-off dust (Ma & Garbers-Craig 2006).
The mechanism of CO bubble bursting in EAF is analogous to bubble bursting in
BOF-converter. Guézennec at al (2005) found out mechanism of droplet ejection follows
three steps shown in Figure 16 and is similar in steel-CO system and air-water-system.
(Guézennec et al. 2005)

Fig 16. Burst of the bubble on a liquid surface (Guézennec et al. 2005).

Mechanism shown in Figure 16 generates two types of drops, film drops and jet

55
drops. Jet drops are larger in size and usually fall back to the liquid bath. Film drops are
more numerous and smaller than jet drops, which enables them to leave to leave with
EAF exhaust gas and contribute to total amount of EAF dust emission. (Guézennec et al.
2005)

3.3.3 Preventing dust generation

The amount of dust generated in mechanism proposed in Figure 16 is dependent on CO2

bubble size. Larger the bubble size is, the more dust is generated in EAF. The bubble
size can be reduced by better control of decarburization reaction. (Guézennec et al.
2005) The second method to reduce dust generation is to reduce oxygen blowing, which
reduces CO bubble generation. Other methods for preventing dust generation include
promoting fast and foamy slag generation and bottom injection of additives and fluxes,
which reduces amount of direct fly-off particles. (Ma & Garbers-Craig 2006)

3.3.4 Disposal of EAF dust

There are four different ways to process dust generated in electric arc furnace, briquetting
or pelleting, direct injection back to EAF, reprocessing to recover valuable components
and disposal to landfill (Zunkel 1997). In previous decades especially low-Zn content
dust was deposited with no further processing. Increased legal requirements for deposit-
ing of hazardous components containing dusts and increase in economic feasibility of
Zn recovery have made recycling and reprocessing of dust more feasible. (López &
López-Delgado 2002) Survey done in USA in year 2000 showed that 54 % of the total
quantity of EAF dust is recycled or reprocessed and the rest is deposited to landfill
(Liebman 2000).

3.3.5 Recycling back to EAF

The two main purposes of EAF dust recycling are to reduce amount of dust leaving the
process and to increase zinc content in dust. The injected dust will melt and blend to
slag layer in EAF, which in turn can be reused in a ways described in EAF slag section.
Easily volatilized agents like zinc, lead, cadmium, chlorine and alkali metals do not
leave with the slag but accumulate in dust. Increase of dust zinc content makes recovery
of zinc more feasible, but accumulation of different agents may cause various problems

56
in process. (Kashiwaya et al. 2004)
The main problem with direct dust injection is accumulation of dust in filtration
system. One way to reduce dust amount is to ensure injected dust does not leave as a
direct fly-off with off-gasses, but goes to slag instead. This can be done by briquetting or
pelleting dust before injection. (Ma & Garbers-Craig 2006) In the same time reducing
agents like coke or ferrosilicon can be added to recover some of the metals in dust. This
in turn increases metal yield of EAF-process. (López & López-Delgado 2002)
One major problem caused by recycling is dust sticking in dust filtering system.
Accumulation of HCl and ZnCl2 in dust promotes to dust adhesion to filters. (Kashiwaya
et al 2004) The accumulation of HCl and other volatiles also increases the corrosion of
the off-gas duct significantly. These effects make dusts containing high amounts of
volatile components unsuitable for recycling to EAF. (Ma & Garbers-Craig 2006)
Recycling of dust back to EAF has been found economically viable for some
companies and has been tried in many steel mills (Ma & Garbers-Craig 2006, Kashiwaya
et al. 2004). Overall the disadvantages of EAF dust recycling have been found quite
small if it doesn’t cause problems with filtration system of the plant. The use of
briquettes may even improve EAF slag conditions by increasing slag foaming. (López &
López-Delgado 2002) The feasibility of recycling is further enhanced if plant already
has pelleting or briquetting capacity suitable for EAF dust processing (Gudenau et al
1999).

3.3.6 Reprocessing

The Main interest of EAF dust reprocessing lies in recovery of zinc. After recovery of
the zinc the hazardous lead and cadmium are removed or modified to a non-leachable
form. Remaining material can then be disposed or re-used as an infrastructure material.
Compositions of EAF dust are quite near BOF-dust so they can be reprocessed in same
plants. (Gudenau et al. 2000) Methods for dust reprocessing are explained in greater
detail in BOF-dust section.

3.3.7 Disposal to landfill

Direct disposal to landfill has previously been the cheapest way to dispose of EAF dust
with low zinc content, but trend in the world is that legislative specifications of material
suitable for disposal are getting tighter and landfilling fees are rising. In some cases the

57
EAF dusts are considered hazardous material due to high content of leachable metals
like Zn, Pb, Cd and Cr. Usually the dust has to be rendered inert before depositing to
landfill (López & López-Delgado 2002). Recycling and reprocessing may decrease
amount of dust but eventually the remaining dust has to deposited or sold off as a new
product (Zunkel 1997).

3.4 Environmental aspects of EAF off-gas

EAF off-gas consists mainly of components of leak air and products of oxidation. Off-gas
has high amount of CO and CO2 because of burning of coke and steel decarburization.
Other notable elements are hydrogen, nitrogen and argon. Oxygen content of off-gas
is usually low because of presence of hydrogen and CO. (Kühn et al. 2005) Off-gas
also contains small amounts of NOx , VOCs and dioxins, which are toxic and can cause
environmental issues (Jones et al. 1998).

3.4.1 CO and CO2

CO and CO2 are an environmental concern since they are greenhouse gasses. They are
formed in process of oxidation of carbon, which is introduced in to an EAF via addition
of coke or as a component of scrap steel. Increased awareness in global warming is
putting pressure on decreasing CO2 emissions from steel industry. Although producing
steel from scrap in EAF produces some CO2 emissions, the amounts are far less than in
steelmaking involving reduction of iron oxides in blast furnace. The main reason for this
is that the scrap used in EAF is already in reduced state, so coke is not needed in high
amounts as a reducing agent. (Birat et al. 1999)
The coke is used in EAF for reducing oxidized metals in scrap and to reduce amount
of electricity used in scrap melting. These advantages of coke addition far outweigh the
possible costs of CO2 emissions, so the amount of CO2 generated is not considered
in EAF operations. The main load of carbon oxide in EAF steel production doesn’t
come from the off-gas but from producing the electricity used in melting of the scrap.
Increasing the portion of the renewable energy generation is the best way to reduce EAF
emissions in single plant, but is hard to implement in global scale. (Birat et al. 1999)
Consumption of electricity can be reduced by increasing the CO2 /CO-ratio of the
off-gas. CO is an intermediate product of carbon combustion and it leaving EAF in
off-gas wastes potential chemical energy of carbon. It has been found out that the

58
CO2 /CO-ratio can be increased by ensuring coke first carburizes the metal bath. The
possible explanation for this effect is that in steel decarburization the carbon oxide
generation occurs at comparatively low rate at large area, which provides favorable
conditions for carbon monoxide post-combustion. CO2 /CO-ratio of off-gas is strongly
affected by oxygen content of the EAF atmosphere, so the process can be enhanced
by blowing oxygen to steel bath. The oxygen blowing also reduces carbon and other
unfavorable tramp element levels to suitable levels for further processing. (Kühn et al.
2005)
A big environmental impact of off-gas comes from the energy it takes away from
EAF. The temperature of steel melt in EAF has to reach certain level to ensure complete
melting of the scrap and energy leaving with off-gas has to be supplied to EAF. (Kühn
et al. 2005)

3.4.2 NOx , VOCs and dioxins

Off-gas also contains small amounts of NOx , VOCs and dioxins as mentioned above.
Although their amount might be small, these gasses are environmentally hazardous and
their amount in off-gas has to be controlled.
NOx is one of the major pollutants besides CO and CO2 in EAF off-gas. Amount
of NOx emissions vary between different EAFs, variance between 4 different EAF
measurements was from 0,015 to 0,78 kg/t scrap used. Reason for this variation is that
formation of NOx is strongly dependent on composition of furnace atmosphere. (Pfeifer
et al. 2012) NOx formed when nitrogen passes through the electric arc and also when
post-combustion of off-gas rises temperature enough to reach level of NOx generation.
Both of these effects can be suppressed when amount of leak air to EAF is reduced.
(Jones et al 1998) Generation of NOx can also be suppressed when oxygen supply to
furnace is kept at minimum (Pfeifer et al. 2012).
Volatile organic compounds (VOC) in EAF off-gas come from organic components
(oil, grease) in scrap. Amount of VOC emission can be reduced by either removing
organic component prior to scrap charging with washing or by ensuring VOCs burn in
EAF. VOC combustion in EAF is beneficial since it provides more chemical energy
to the EAF and it can be promoted with addition of excess oxygen to the electric arc
furnace (Jones et al. 1998).
Dioxins and furans are extremely toxic even in small quantities and they have
become a major environmental concern in incineration processes. A study conducted

59
in Taiwan for area containing many different steelmaking and incineration processes
showed that dioxin content of ambient air was mostly affected by EAFs and sinter plants.
(Wang et al. 2009) Generation of dioxins is related to combustion of chlorine containing
material and is strongly catalyzed by copper. Effectiveness of copper catalyst is further
enhanced by Al2 O3 . These conditions are met quite precisely in off-gas stream of EAF.
(Jones et al. 1998) The generation of dioxins is further enhanced by pre-heating of the
scrap which rises amount of organic compounds of incomplete combustion (Friedacher
et al. 2006)
Dioxin generation is strongly influenced by temperature; their generation is believed
to happen at temperature of approximately 500 ◦ C (Jones et al. 1998). Generation of
dioxins can be reduced by avoiding the said temperature region by cooling off-gas
rapidly with spray water. The other way to reduce dioxin emissions significantly is
to use post combustion chamber in which dioxins and other organic components are
destroyed by heating (>850 ◦ C). Efficient dust filtering also reduces amount of oxygen
released to atmosphere. (Friedacher et al. 2006)

60
4 Environmental aspects of BOF slag and dust
Authors: Petri Sulasalmi and Ville-Valtteri Visuri

4.1 Basic oxygen furnace

Basic oxygen furnace (BOF) is a process in primary steelmaking, in which steel is

produced from high-carbon pig iron by oxygen blowing. The name of the BOF process
stems from two properties: basic refractory lining and oxygen blowing. Oxygen is
delivered at supersonic velocity with the help of a water-cooled lance fitted with a de
Laval nozzle. (Deo & Boom 1993)
First succesful test with a BOF converter was conducted in 1948 by Prof. Robert
Durrer (ETH Zürich). In 1952–1953, the process was commercialised in Austria
by VÖEST in Linz and ÖAMG in Donawitz in cooperation with Gesellschaft der
Ludwig von Roll’schen Eisenwerke in Switzerland. Hence the process is also known as
Linz-Donawitz (LD) process. (Deo & Boom 1993)
Although the BOF was originally a top-blowing process, numerous combined-
blowing variants have also been introduced. Deo & Boom (1993) have listed the main
categories for combined-blowing processes as follows:

1. Top-blown oxygen and inert stirring from the bottom

2. Top-blown oxygen plus inert and oxidising gasses from the bottom
3. Combined oxygen top- and bottom-blowing
4. Fired blowing processes, in which the scrap is first melted

An example of the first category is the Linz-Donawitz Kawasaki Gas (LD-KG) process,
in which oxygen is blown from the top lance, while stirring gases are delivered from the
bottom nozzle plate (Figure 17). In Finland, three converters of this type are currently
in operation at Ruukki Metals Raahe Steel Works. The basic oxygen furnace uses no
additional fuel. The pig iron impurities (carbon, silicon, manganese and phosphorous)
serve as fuel. Iron and its impurities oxidize evolving heat necessary for the process.
Oxidation of the molten metal and the slag is complicated process proceeding in
several stages and occurring simultaneously on the boundaries between different phases
(gas-metal, gas-slag, slag-metal). Finally the reactions may be presented as follows:
(Deo & Boom 1993)

61
Fig 17. Combined-blowing converter (Metallinjalostajat ry 2009)

1
O2 (g) = O (2)
2
1
Fe + O2 (g) = (FeO) (3)
2
Si + O2 (g) = (SiO2 ) (4)
1
Mn + O2 (g) = (MnO) (5)
2
5
2P + O2 (g) = (P2 O5 ) (6)
2
1
C + O2 (g) = CO(g) (7)
2
1
CO(g) + O2 (g) = CO2 (g) (8)
2
Most oxides are absorbed by the slag. Gaseous products CO and CO2 are transferred
to the atmosphere and removed by the exhausting system. Oxidizing potential of the
atmosphere is characterized by the post-combustion ratio: (Deo & Boom 1993)

CO2 (g)
(9)
CO2 (g) +CO(g)
Basic Oxygen Process has limiting ability for desulfurization. The most popular method
of desulfurization is removal of sulfur from molten steel to the basic reducing slag.
However the slag formed in the Basic Oxygen Furnace is oxidizing (not reducing)
therefore maximum value of distribution coefficient of sulfur in the process is about 10,
which may be achieved in the slags containing high concentrations of CaO. (Deo &
Boom 1993)

62
4.2 Basic oxygen furnace slag

The terms “BOF steel slag“ and “BOF slag“ are not interchangeable: the term “BOF
steel slag“ refers to the molten slag formed in the process, while the term “BOF slag“
refers to slag after its solidification (Motz & Geiseler 2001).
Typical BOF slags are calciumsilicatic: the main mineral phases are dicalciumsilicate,
dicalciumferrite and wustite (Figure 18). Main constituents are CaO and SiO2 , ranging
between 42–55% and 12–18%, respectively. Other important oxides are FeO, Fe2 O3 ,
Al2 O3 and MnO. The BOF slag is highly heterogeneous in chemical composition, and
the geometrical shape and size of the pores, pits, vacancies and steps vary likewise.
(Chaurand et al. 2006, Koch et al. 1984, Li 1999, Motz & Geiseler 2001, Xue et al.
2009).

Fig 18. SEM backscattered electron image of a BOF steel slag (polished section,
grains of 200–500 µm (Chaurand et al. 2006).

The initial slag formed in the process is rich in FeO and SiO2 . The slag starts to
foam when approximately 30–40% of the blow is passed, resulting in decreasing FeO
content. The foaming reaches its maximum around 50-60% of the blow. At this point
the decarburisation rate starts to fall, due to which more oxygen is consumed by the
formation of FeO. (Deo & Boom 1993)

4.2.1 Production and environmental concerns

Roughly 100–150 kg of slag is produced per ton of crude steel in the production of
liquid steel in a Basic Oxygen Furnace (Reddy et al. 2006). In recent years, more
and more emphasis has been put on the management of the BOF slag due to the vast
quantities generated by the steel industry (Xue et al. 2009).
China is by far the biggest producer of steel slag with an annual output of roughly 17

63
million tons (Xue et al. 2006). Different figures have been presented for the utilisation
ratio, ranging from “lower than ten per cent“ for the BOF slag (Wang & Yan 2010)
to 80% for all steel slags as suggested by Xue et al. (2006). In India, some 4 million
tonnes of BOF slag is generated annually (Reddy et al. 2006).
Europe is the second largest producer of steel slags. In 2004 the European steel
industry produced roughly 15 million tons of steel slag, from which 62% were BOF
slags (Böhmer et al. 2008). Approximately 75% of the produced steel slags are put in to
use, while the rest is dumped (Böhmer et al. 2008b). The average dumping rate varies
greatly by country: in Germany, for instance, the dumping rate is less than 10%. (Motz
& Geiseler 2001).
In the United States, the production of BOF and EAF slag has been on decline,
decreasing from estimated 8 million tonnes in 2006 to estimated 6 million tonnes in
2011 (U. S. Geological Survey 2011).
As such, the BOF-slag is often considered as a by-product or simply waste (Reddy
et al. 2006, Chen et al. 2011). However, the BOF slag may be processed further to
enable use in civil engineering.
Organic substances do not exist in slags due to high melting temperatures (Motz
& Geiseler 2001). The concentrations of heavy elements in the slag are low, albeit
chromium may be found in somewhat higher amounts (Motz & Geiseler 2001). In a
study conducted by Proctor et al. (2000) it was concluded that not even the maximum
concentrations of metals in the BOF samples exceeded the U.S. EPA standards for
determining slag as characteristically hazardous.
The chromium in steel slags is bound in stable crystalline phases Cr is present in
its trivalent form, which is not as mobile or toxic as the other forms. Cr also remains
in the trivalent form during leaching. However, the vanadium in the BOF slag is
predominantly present in a toxic quadrivalent form. Unlike chromium, vanadium is
released significantly. Furthermore, vanadium oxidises to its most toxic pentavalent
form during natural ageing and leaching. (Chaurand et al. 2006, 2007)
Methods for decreasing leaching of elements have also been studied. Tossavainen
et al. (2007) studied rapid cooling of BOF slag and concluded that leaching of minor
elements cannot be prevented by rapid cooling as the BOF slag has a very low tendency
of glass forming.
Windt et al. (2011) have proposed a model for simulating e.g. the kinetically
controlled dissolution of primary and secondary phases and progressive release of
elements in BOF slag. Various methods have been proposed for recycling the slag, e.g.

64
use of slag as input material in sinter making or in a blast furnace (Chen et al. 2011).
Figure 19 illustrates the flow charts of three different treatment and recycling processes.
The environmental and mechanical properties of BOF slag can also be improved by
reduction of slag (Ye et al. 2003).

Fig 19. Flow charts for the treatment and recycling processes of steel slag: a) hot
splashing technology b) water quenching c) water quenching + wind quenching
(Chen et al. 2011).

65
4.2.2 Use in civil engineering

According to (Motz & Geiseler 2001), the most important technical properties of BOF
slags for civil engineering are:

1. bulk density
2. shape
3. resistance to fragmentation
4. strength
5. water absorption
6. resistance to freezing and thwawing
7. volume stability
8. resistance to abrasion and polishing

Motz & Geiseler (2001) argue that the free lime and MgO contents are the most
important factors for utilisation of BOF slags in civil engineering. When in contact
with moisture, they form hydroxides, which deteriorate the slag properties by causing
volume increase, distintegration of slag and loss of strength (Böhmer et al. 2008b, Motz
& Geiseler 2001, Shen et al. 2009). If the free lime content is above 7% the slag usually
cannot be used as building aggregates (Böhmer et al. 2008b).
There are methods for stabilising the BOF slag, such as adding silica sand combined
with oxygen blowing, ageing by steam with or without pressure or ageing by spraying
with water and carbonation, i.e. heating the slag in air with CO2 (Böhmer et al. 2008b,
Mikhail & Turcotte 1995). The technical properties of processed steelmaking slags in
comparison to established natural aggregates are presented in Table 10.
BOF slag has been used as an aggregate in asphalt pavement in many countries.
Previously, the main limiting factor has been the expansive nature of the BOF slag.
(Mikhail & Turcotte 1995, Motz & Geiseler 2001). Xue et al. (2006) have studied the
use of BOF slag aggregate in asphalt pavement and concluded that comparable with or
even superior than conventional asphalt pavement and that BOF slag may be used even
in asphalt concrete. Although the BOF slag provides the hot mix asphalt with high
stability, good stripping resistance and excellent skid resistance, it increases the demand
for asphalt binder due to its porous nature (Shen et al. 2009).
In the 1970s, test roads were build in Germany in cooperation between steel
producers and road building administration. From these test roads, it was found that
the aggregate mixtures are permanently stable, although certain requirements for the

66
Table 10. Technical properties of processed steelmaking slags and established
natural aggregates (Motz & Geiseler 2001).

Characteristics BOF-slag EAF-slag Granite Flint gravel

Bulk density (g/cm3 ) 3.3 3.5 2.5 2.6
Thin and elongated pieces (%) < 10 < 10 < 10 < 10
Impact value (%/wt.) 22 18 12 21
Crushing value (%/wt.) 15 13 17 21
10% fines (KN) 320 350 260 250
Polishing (PSV) 58 61 48 45
Water absorption (%/wt.) 1.0 0.7 < 0.5 < 0.5
Resistance to free-thaw (%/wt.) < 0.5 < 0.5 < 0.5 <1
Binder adhesion (%) > 90 > 90 > 90 > 85
volume stability have to be met. Despite heavy traffic, the asphaltic surface remains
permanently plain and the long-term resistance to polishing is high. The processed steel
slag aggregate mixture provides a stronger bearing capacity directly after compaction
than the other aggregates. The bearing capacity, which is increased by carbonatic
solidification, is not affected by heavy rain. The leaching of unbound or bituminous
bound aggregates has been found insignificant. (Motz & Geiseler 2001)
Production of ternary blended hydraulic road binder mixing BOF slag, ground
granulated blast furnace slag (GGBFS) and catalyst has been tested with good results
(Mahieux et al. 2009).
Production of Portland cements is an energy intensive process involving grinding
and calcinations of raw materials and grinding of cement clinker and gypsum. As the
BOF slag requires only grinding, considerable amounts of energy can be saved with the
use of BOF slag in Portland cement (Shi & Qian 1999). Both EAF slag aggregates
(Maslehuddin et al. 2003) and BOF slag aggregates (Reddy et al. 2006, Monshi &
Asgarani 1999, Shi & Qian 2000) are well-suited for substituting natural aggregates in
Portland cement. Shi & Qian (2000) suggest that instead of using BOF slag as bulk slag
aggregates, it should be used as partial of full replacement for Portland cement.
High bulk density enables the use of slag as a construction material for hydraulic
engineering purposes, e.g. for dams, stabilisation of river banks and bottoms and refilling
of erosion areas on river bottoms. In Germany alone, roughly 400,000 tons are used
annually for such purposes. (Motz & Geiseler 2001)

67
4.2.3 Use in water treatment

It has been shown that BOF slag can be used for fluoride (Islam & Patel 2011) and
phosphorus (Xue et al. 2009) removal in waste water treatment. The abundant calcium
and aluminium ions in the treated slag enhance the processes of adsorption and chemical
precipitation, which help to remove pollutants. (Xue et al. 2006)
Two main adsorption mechanisms for adsorption of fluoride onto slag have been
identified: ligand exchange and precipitation effect. Xue et al. (2006) have suggested
that ligand exchange is the dominant mechanism in the adsorption mechanism of
phosphate onto the BOF slag. It has been found that the increasing pH to decreases the
phosphate adsorption by the slag. A strong dependency between surface characteristics
and phosphate adsorption has also been observed. (Xue et al. 2006)
Polluted and contaminated water often contains heavy metal species, which are
detrimental to many living species due to their tendency to accumulate in the system.
BOF slag has the ability to absorb common heavy metals, such as copper, cadmium,
lead and zinc, from waste water (Xue et al. 2009).
The use of BOF slag and hydrogen peroxide (H2 O2 ) to degrade 4-chlorophenol
and its oxidation intermediates has been studied by Li (1999). It was concluded that
4-chlorophenol can be completely decomposed by BOF slag with H2 O2 in an acid
solution. The main advantages of BOF slag in this purpose are its reusability and high
treatment efficiency. (Li 1999).

4.3 Basic oxygen furnace dust

This section gives insight into basic oxygen furnace dust. Other dusts have been treated
alongside to corresponding process. BOF dust is the second largest solid-waste residue
generated by the integrated steel mills. This byproduct, which is collected as flue
dust during the steel production in BOF, contains over 50% iron in the form of oxides.
(Mikhail & Turcotte 1997) In BOF (and also in electric arc furnace) process the flue
gasses, which contain solid particles, i.e. BOF dust, are collected and directed to wet
cleaning process. As a result of wet cleaning, considerable degree of dust is recovered
from the gas. The fine solid particles recovered after wet cleaning of the gas emerging
from BOF converters in the sludge form are termed as BOF sludge. Roughly 15–16 kg
of BOF sludge is formed per ton of steel in a BOF process (Havlík et al. 2006, Das et al.
2007c). It is estimated that each year, 5–7 million tons of BOF sludge is generated

68
worldwide (Sammut et al. 2008).

4.3.1 Dust formation mechanisms in BOF process

Four mechanisms contributing to dust formation can be considered: 1) ejection of

metal droplets, 2) ejection of slag droplets, 3) entrainment of charged material and
4) vaporization. Nedar has studied the dust formation in BOF process at the SSAB
Tunnplåt AB Luleå. The study concluded that the most significant mechanism is the
ejection of metal and slag droplets from the bath. The total contribution by these two
mechanisms was around 67% but it also shows that the other sources aren’t negligible as
they form approximately 30% of the dust.
The dust formation was studied in two parts of the oxygen blowing. During the
first part lime or dolomite lime was charged into the converter, during the second part
nothing was added in the process. It showed that the ejection of metal dominated the
dust formation in the initial stage of blowing while ejected slag made a significant
contribution in the latter part. Origins of the ejected material were splashing or CO
bubbles which burst when reaching the surface and created droplets. Charging material
created dust the most dust in the beginning of the blowing when the slag forming
materials is added. Large part of the dust was created by vaporization, in average 17%
of the dust from the first part and 32% from the second part. Zn, Pb and Cl are easily
vaporized elements and were found from the early part dust while Mn and Cu were
found in the samples at the end. Na and K were present in the samples from the second
part. These elements sourced from alkali rich slag former. (Nedar 1996)

4.3.2 Composition of BOF dust

The principal component of BOF dust is iron. Recovering and recycling iron units,
as well other valuable elements e.g. zinc, may result in a significant energy and raw
material savings. It also has its effect on reducing waste along with other environmental
benefits. In addition to Fe, Mn and Pb, the presence of Zn in the BOF dust emissions has
been clearly demonstrated. (Sammut et al. 2008) BOF dust also contains silica, calcium,
magnesium and other minor elemental oxides in lesser amounts, an example of a BOF
dust sample is presented in Table 11. Chemical analysis of a typical sludge sample are
presented in Table 12, while a typical size and elemental distribution is presented in
Table 13. (Mikhail & Turcotte 1997)

69
Table 11. BOF dust sample.

Component wt-%
Fe 59
Ca 7.4
Mg 2.1
Mn 2.1
Zn 1.5
SiO2 1.2
C 0.5
Table 12. Chemical analysis of a typical sludge sample (Das et al. 2007c).

Sample 1 Sample 2
Constituents wt-% wt-%
Fe (total) 64.12 61.0
FeO 79.58 76.93
Fe2 O3 2.79 1.43
CaO 8.9 10.59
MgO 0.38 0.38
SiO2 0.71 1.97
Al2 O3 0.32 0.95
P 0.101 0.126
MnO 0.10 0.24
Table 13. Size and elemental distribution of a sludge sample (Das et al. 2007c).

Size (µm) (wt-%) Fe Acid Ins CaO

+1000 9.8 65.34 0.79 9.75
+500 12.9 63.7 0.40 9.0
+300 4.0 65.34 0.58 8.75
+150 4.4 62.82 0.80 9.5
+75 0.5 61.9 1.21 13.0
+45 6.8 63.38 1.29 10.0
-45 61.6 64.2 0.69 9.5
Head 100 64.16 0.71 8.62
4.3.3 Pre-processing methods

Removal of unwanted components from steel making process dusts targets to recycling
the dusts back to processes as the dusts contain useful amounts of different iron oxides
and carbon. Extracting zinc is one of the main obstacles in preprocessing dust or sludge.

70
Low vaporization temperature of zinc causes it to accumulate in the furnace off-gasses
in the form of small dust particles whether it is blast furnace (BF), basic oxygen furnace
(BOF) or electric arc furnace (EAF). Regardless of the source, build-up of zinc in the
steel making processes is not desirable due its adverse effect on the process performance
and eventual quality of steel. (Kelebek et al. 2004)
Zn originates from the recycled scrap (e.g. cars, cans, bridge, building, etc.) used
as a secondary source of iron in the BOF process. Removal of Pb and alkalis is also
important in order to recycle the dusts back to processes. The moisture content of
dusts from different sources varies greatly, from 0–98%, which has to be taken into
account when considering the preproduction process. At steel plants, the high moisture
content of the BOF sludge (35–40%) is a major obstacle in its recycling to the sinter
plant. It becomes sticky and forms agglomerates after long exposure to the atmosphere.
Therefore, BOF sludge has to be optimally dried and made handleable before recycling
(Das et al. 2007c). Same naturally applies to other process dusts which has a high
moisture content.

4.3.4 Recovery of Zn and Pb

Zn as well as Pb content of different dusts varies. For example, EAF dust is very rich
in zinc content (>20%) compared to BOF dust (1–3%), blast furnace flue dust zinc
content is even smaller (Kelebek et al. 2004, Das et al. 2007c). Das et al. (2007) have
reported plenty of different methods for recovering Zn and Pb in their overview. A
hydrometallurgical process whereby the sludge is leached under both acid and oxidizing
conditions has been reported. Hydrometallurgical processes have also been carried out
with EAF and BOF dusts to recover Zn.
After the separation of the solids, i.e. carbon and iron from the leaching solution, the
latter is passed through an anion exchanger to remove Zn and Pb and then recirculated
to the reactor. In some cases selective leaching by sulfuric acid at low concentration and
room temperature, gives rise to high recovery of zinc (about 80%). Investigation has
been carried out on the use of the NH4 SCN solution. ZnO reacts with NH3 SCN and
forms Zn(SCN)2 which dissolves easily in water.
Zn from Zn-bearing blast furnace wastes is also separated by froth flotation and wet
cyclone methods. Experiments have shown that Zn, Pb and other nonferrous metal
contents of blast furnace dust can be removed by wet-classifying the dust in a cyclone
separator. In another attempt by oxidizing–chlorination roasting of blast furnace and

71
steel making converter sludges with CaCl2 for the sublimation of Zn and Pb chlorides it
was observed that the degrees of Zn and Pb chloride sublimation were 99.48% and
98.58%, respectively.
A study was made for the reduction of iron oxides and zinc compounds by the
carbon contained in sludge with simultaneous removal of Zn from high-zinc blast
furnace sludge. Briquettes of the sludge were fired for different times and at different
temperatures. Beside the degree of metallization of iron and removal of zinc it was also
possible to evaluate the utilization of carbon contained in the sludge.
The use of Waelz kiln (rotary kiln) to reclaim Zn and Pb from blast furnace sludge
has been attempted. The material is premixed in wagons, fed into an impact crusher,
pelletized and finally put into the kiln. Water, hydrate of lime and coke breeze is added
as needed since carbon and basicities help dezincing and reduction of iron oxide. It was
possible to volatilize successfully 95% Zn, 95% Pb, 30% sulfur and 30% potassium
oxide from a mixture containing 44% Fe, 4.5% Zn, 2% Pb and 7% carbon. About 80%
of the final product was 5 mm in size and would have to be sintered. (Das et al. 2007c)
At Nippon Steel Kimitsu Works, a high temperature process for recovering Zn has
been developed. Zinc is removed from the pelletized raw material by using a rotary
hearth furnace (RHF). The raw material pellets that are feed from the feeder are carried
by the moving floor to the heating zone, where they are heated to 1.000 ◦ C or higher.
Then, in the reduction zone, the pellets reach the reaction temperature, which is greater
than 1,100 ◦ C, and the reduction of zinc oxide and iron oxide by carbon takes place.
Here, as the zinc evaporates from the pellets, the zinc removal reaction proceeds. The
surplus carbon monoxide is utilized as thermal energy through secondary combustion.
This method has the following benefits: 1) Production of agglomerates that can be put
into the RHF directly without requiring pre-drying, 2) the process is hardly influenced
by sludge properties and hence can be applied to a wide variety of sludge materials and
3) the process is capable of removing alkalis and other water-soluble substances from
raw material sludge, making it possible to improve the sludge properties. Figure 20
clarifies the RHF process. At Kimitsu Works they have two RHFs for different dust and
sludge types to choose from depending on the moisture content of the input material.
Figure 21 shows the material flow of dust and sludge (Oda et al. 2006).
A study for extracting zinc from EAF dust was carried out where Zn was leached
using H2 SO4 . The study concluded that Zn removal was dependent on sulphuric acid
concentration: The maximum extraction (around 75%) was achieved by using concen-
trations higher than 0.5 mol L−1 H2 SO4 . Leaching of Zn was relatively independent

72
Fig 20. The structure of RHF (Oda et al. 2006).

Fig 21. Material flow of dust and sludge at Kimitsu Works (Oda et al. 2006).
from temperature, although, the maximum extractions of zinc were achieved at lower
temperatures (Havlík et al. 2006).
Another research for recovering Zn from EAF dust was made in which the objective
of the process studied is to extract zinc from zinc ferrites contained in EAF dusts without
destroying the iron oxide matrix, which can be recycled in the steel industry. The
process wass a hydrometallurgical treatment of waste based on the destruction of the
ferrite structure. For this, ZnFe2 O4 is treated by FeCl3 ·6H2 O. The reaction consists of

73
O2 –/Cl– exchange allowing the recovery of zinc as ZnCl2 and iron as hematite Fe2 O3 .
The separation of these products was obtained by aqueous leaching. In a first step, the
process was studied on zinc ferrites synthesised in the laboratory, then extended to
real samples. All the zinc is extracted after a 8 h treatment at 150 C with a molar ratio
FeCl3 ·6H2 O/ZnFe2 O4 of 10 (Leclerc & Lecuire 2003).
Cantarino et al. presented a hybrid treatment method for BOF sludge. The study
characterized the fine and coarse fractions of BOF sludge, and a method for the selective
removal of zinc was investigated. Iron was found as a predominant species in both
fractions of the sludge (50.65% in the fine and 67.61% in the coarse fraction), while zinc
was found mainly in the fine fraction (4.37% and 0.51% in the coarse fraction). The
effect different material and reagents to zinc removal from the fine fraction of BOF
sludge with three leaching steps was compared (see Figure 22). The leaching with
NaOH was found to be very selective to zinc over iron. Also the temperature dependence
(see Figure 23) to leaching with NaOH was studied. (Cantarino et al. 2012).

Fig 22. Effect of different reagents to Zn removal (Cantarino et al. 2012).

At MEFOS, Luleå, a grinding and dehydrating process, Tornado, has been tested for
number of metallurgical applications. The materials tested ranged from metallurgical
slags containing 2–3% moisture to sludges with up to 70% moisture. The process
consists principally of one air fan providing a high-velocity airstream that enters a
mechanical cyclone.
When the gas enters the cyclone, an outer vortex is created. This outer vortex rotates

74
Fig 23. Temperature dependence on Zn removal when leaching with NaOH (Can-
tarino et al. 2012).
next to the cyclone wall, and at the bottom of the cyclone funnel the gas stream is turned
and an inner vortex is created. The control of the air flow is tuned by a special device on
top of the cyclone. The gas outlet is at the top of the cyclone and the material outlet at
the bottom. The material is fed through a feeding device into the airstream channel
prior to the inlet into the cyclone. Figure 24 gives the scheme of Tornado pilot plant at
MEFOS. The process is basically an improved grinding and dehydrating system, which
is very efficient and environmentally friendly and can even be employed with very sticky
materials. Also due to its rotating comminution, the material particles become rounded
during grinding, hence more free flowing and easier to handle (Tikka et al. 2007).

4.3.5 Removal of alkalis

The performance of blast furnace is strongly affected for presence of alkali due to
lowering down the softening and melting temperature of iron ore and sinters. Alkaline
elements accumulate in blast furnace due to cyclic reactions and hinder the normal
operations, loss of permeability of the burden, cracking of refractory bricks, etc. In
addition to this alkali cyanides is likely to be formed cause environmental problems.
(Das et al. 2007c) Thus, removal of alkalis is important before recycling dust of slugde
back to BF process. Removal of alkalis is mandatory also from other dusts for the same
reasons.

75
Fig 24. Scheme of the Tornado pilot plant at MEFOS. (Tikka et al. 2007)
For dealkalification of blast furnace dust, acid leaching has been suggested to
promote increased recycling of iron making. Besides that scrubbing, washing, leaching
with CaCl2 , NH4 Cl, etc. has been carried out. The study carried out at Regional
Research Laboratory, Bhubaneswar, India reveals that it was possible to remove around
75% of Na values by reducing the particle size. However the removal of potassium was
restricted to 22% only (Das et al. 2002b).
In a study done by Zabett and Lu it has been shown that alkali halides and lead
compounds can be vaporized and removed from EAF dust at a temperature as low as
900 C. The separation can be done by the use of a carrier gas or by means of reduced
pressure in a virtually closed system. Oxidizing atmosphere or additives facilitate the
removal of lead in the form of lead oxide, while a reducing condition decreases the
vapor pressure of alkali halides and lead compounds and increases zinc loss due to its
reduction and evaporation. A gasifying agent such as CaCl2 does not help the removal of
alkali halides and lead compounds significantly but increases the zinc loss. For operation
at reduced pressure, the maximum working pressure has been determined and reported
for the system at different temperatures (Zabett & Lu 2008).
The rotary hearth furnace process that was mentioned in the previous section applies
also for the removal of alkalis.

76
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