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Recycling Steelmaking

Slags in Cement
D Satish Kumar, T Umadevi, H K Paliwal, Ganapathi Prasad, P C Mahapatra and
Madhu Ranjan, JSW Steel, India.

Steel industries generate large quantities of slags from their iron-making and steel-making
processes. Iron making slags are recycled in cement making and steel-making slags are
dumped because they are unsuitable for the cement industry owing to the high iron
content and other impurities. Steel making slag is a non-uniform mix of compositional
slags generated at different different stages in the treatment and collectively dumped in a
common pit. With the introduction of a pre-treatment facility, individual slag segregation
and a granulation facility, of which there are few of its kind in the world, the steel melting
shop at the JSW Vijayanagar plant generates five different kinds of slags, each with a
different composition and suitability for recycling. To exploit this advantage, a detailed
investigation was carried out through lab scale studies to estimate the maximum permissible
limits of various individual steelmaking slags in cement making. Experiments were
conducted using these slags independently at different proportions in cement making and
compared for strength and setting time. Among all the slags used, 28-day strength for
granulated LD slag has been found to be 48 MPa and is similar to the present ironmaking
slag cement. This led to the development of a new route of recycling steelmaking slag in
cement making through the process of granulation. Granulated LD slag is presently being
used at JSW cement plant up to 10%.

Introduction
In an integrated steel plant, 2 4 t of wastes (including
solid, liquid and gas) are generated for every tonne of
steel produced. Accordingly, today the emphasis1-5 is on
the avoidance of waste generation, recycling and reuse of
waste, and minimising the adverse impact of disposal on
the environment. Among all the solid/liquid wastes, slags
generated at iron making and steel making units are created
in the largest quantities. With increasing capacities, disposal
of large quantities of slag becomes a big environmental
concern and a critical issue for steel makers. Over the last
few years, with a better understanding of slags, its functions
and improvements in process technologies have led to a

significant reduction in the volume of slag generated. At the


same time, the re-use of iron and steelmaking slags has also
been expanded, and has led to a significant reduction in the
environmental impact of these byproducts2-10. However slag
generation remains inevitable and emphasis on its recycling
remains the greatest concern.
The two biggest wastes generated in an integrated steel
plant are steel slag and iron slag. The iron slag is made in
a blastfurnace, and consequently steel slags are produced
in steel making processes (e.g. basic oxygen furnace,
pretreatment, de-sulfurisation units and sec steelmaking
units). Both the slags are primarily lime based and produced
at different temperatures by different reactions and are

Table 1. Chemical composition of various steel making slags


SiO2

FeO

Al2O3

CaO

MgO

MnO

P2O5

LD Slag

14.22

23.17

0.93

47.80

9.73

0.57

2.34

0.03

Steel slag

4.88

1.59

28.37

50.58

12.25

0.72

0.08

0.32

HMDS slag

1.87

28.62

1.41

46.47

0.57

0.09

2.47

HMPT slag

33.46

5.75

4.67

49.64

2.71

0.73

0.21

0.09

SGP slag

13.50

21.10

0.95

46.50

9.50

0.78

1.86

0.05

BF slag

33.00

0.40

19.00

32.00

10.00

0.20

0.80

Table 2. Free lime percentage in various steel making slags


LD slag

7 8%

Steel slag

6 7%

HMDS slag

3 4%

HMPT slag

3 5%

Granulated LD slag

2 3%

BF slag

Nil

Table 3. Components of steel making slags


Slag

Desirable

Undesirable

HMPT slag

CaO, SiO2

FeO, P2O5

HMDS slag

CaO, SiO2

S, FeO

LD slag

CaO, SiO2

MgO, FeO, P2O5

SGP slag

CaO, SiO2

MgO, FeO, P2O5

Steel slag

CaO, SiO2

MgO, S

associated with different impurities. This makes their


chemistry different and limits individual applications.
Because of high CaO, MgO, SiO2 and Al2O3 contents, these
slags can principally substitute raw materials for cement
production. Iron making slags are significantly utilised
in cement making, but steel slags are discarded due to
their chemical nature or the presence of other unwanted
impurities.
Steel slags have a higher magnesium concentration and
free lime content, which limits its usage in cement/concrete
processes.There is usually more residual metallic iron that
needs to be removed. Unutilised slag is used for land filling
and stabilisation of lower parts of soil. Still steel slag disposal
through land filling is difficult due to non availability of
land, associated cost of treatment and cost of development of
dumping sites
Several attempts have been made by different
companies to utilise steel slag; however the utilisation ratio
is significantly low. LD slags with low phosphorous have
been used back in blastfurnaces10. Italian industrial plant
Ospitaletto Works of Stefana SpA9 converted ladle furnace
slag so called white slag and spent refractory into a
final powder product that can be injected in its Electric Arc
Furnace. The reported benefits of reduced cost for slag
dumping comes from the reduced amount of lime charged
into the EAF. LD slag can be utilized in many areas, such
as soil conditioners, fertilisers, recovery of metal values,
etc. Experiments were reported11 using pulverised LD slag
for growing vegetables like tomatoes, potatoes, onions,
spinach, and crops like wheat, in the acidic soil. The LD
slag of various ages has been used in the construction of the
wearing course of several works and public roads in Japan.
Nippon Slag Association in Japan is researching converter

slag utilisation in port and harbour construction and the use


of EAF oxidising slag as concrete aggregate12. A major area
for utilisation of LD slag is in ballast for railway tracks. The
slag samples from Indian steel plants have been tested and
found to satisfy the railway specifications for ballasts. Most
of the literature2-10 on slag utilisation in cement plants deals
with the experimentation using iron making slags. A few US
plants13 have experimented with several different EAF slags
in cement making and claimed usage to an extent of 4 12%
and also reported profits in terms of cost reduction. However
the extent of usage for steelmaking slag in roads construction
and similar applications is limited because it is prone to selfdegradation, a characteristic caused by presence of free lime
in the slag and its hydration ability accompanied by volume
changes. Some methods to overcome this obstacle is natural
ageing of the demetalised slag at an outdoor yard. The
process takes 6 9 months. To shorten the ageing time, a few
processes were developed in Japan, Germany and Brazil14, 15.
Most of the work on slag recycling was based on experiments
with combined steel slag. Steel making plants normally
generate different slags in varying proportions and dump
them in a common slag pit. This paper aims to develop
a methodology of utilising the steel slag by segregating it
according to its nature and increasing its utilisation in cement
making.

Steelmaking slags at JSW


The 7 million tpa steel unit at Vijayanagar works generates
5500 tpd of iron making slag and 3200 tpd of steel
making slag. A portion of iron making slag is utilised in
cement making; the rest of the iron making slag is sold.
The combined steel making slag is completely dumped
or used for ground filling after crushing. Earlier trials at
JSW have shown that steel making slag can be used up to
40kg/t in COREX and 50 kg/t in blastfurnace and this is in
practice. Steel making slag was also experimented with as a
replacement for limestone in pellet and sinter plants up to
around 10 kg/t and 30 kg/t respectively. However, with the
increasing capacities, the disposal of such huge quantities of
steel slag is a real challenge.
JSW Steels Vijayanagar works has unique steel
making facilities with hot metal pre-treatment and LD slag
granulation facilities in place, which are one of very few
in the world and the first of its kind in India. Accordingly,
steel melting work at JSW Vijayanagar plant generates five
different kinds of slag, as shown in Figure 1.
ll HMPT - Hot metal pre-treatment (30 kg/t)
ll HMDS - Hot metal de-sulfurisation (2 kg/t)
ll LD - Converter (180 kg/t)
ll LHF (Steel) - Ladle heating furnace (23 kg/t)
ll SGP - Slag granulation plant (80 120 kg/t)

Figure 1. Steel making process and slag generation points.

It is worth mentioning that slag


generated from SGP is the converted LD
slag and its quantity depends upon the
quantity of LD slag processed through the
SGP.
Each slag has a different composition,
morphology (Figure 1) and suitability
for recycling. It is conceived that, instead
of dumping all the slags in a common
pit, if segregated and used separately, its
recycling percentage can be increased.
Slags have been recycled to a limited
extent in cement making in some previous
trials, due to the limitation of BOF
slag composition. A detailed study was
required to check the usability of these
Figure 2. Steel making slags.
slags independently in a cement plant at
higher limits. No specific information or
trial details are available in open literature
ll LD slag: These slags are a well mixed aggregate of FeO,
on the independent use of these different slags in cement
lime, silica and MgO generated at the LD converter. They
making. The present project was first of its kind and was
are in the form of di-calcium and tri-calcium silicates.
expected to develop feasible strategies for SMS recycling.
These slags also contain free lime and metal, which
The five different slags generated at various points of
creates problems due to expansion characteristics.
the steel making process are described below and shown in
ll Steel slag: These slags vary in composition with respect to
Figure 2.
the varied treatment. The common steel slags are fused
ll HMPT slag: This slag is primarily the slag generated
calcium aluminates with less than 2% (FeO + MnO).
after de-siliconisation or de-phosphorisation treatment.
These readily crumble to dust due to allotropic phase
It has a high content of silica and lime. Sometimes it also
transformation at lower temperatures and are difficult to
contains BF slag.
manage.
ll HMDS slag: This is the raked slag at the de-sulfurisation
ll SGP slag: LD slag is subjected to granulation through
station. These slags are poorly mixed composites of
a quenching technology adopted at JSW, which houses
spilled BF slag, spent and/or unreacted de-sulfurisation
the first of its kind in India. Due to sudden quenching,
agents, lime fines and trapped droplets of hot metal and
of the molten slag, contraction of metal and slag occurs
raked iron.

and results in good separation of metal and slag.


Adequate granulation takes place and leads to good
stability of the final slag. Process can be described as an
accelerated ageing process that reduces the free lime
content. Because of rapid cooling it generates more glassy
structure than the BOF slag. Removal of free lime also
confirms its volumetric stability.

Table 4. Cement specifications


Chemical requirement
Free Lime *

<4%

FeO

Minimum

SO3, %

Max 3.0

Insoluble residue (IR), %

Max 5.0

MgO, %

Max 8.0

Loss on ignition (LOI), %

Max 5.0

Sulphide sulphur, %

Max 1.5

Slags in cement making


Converter slags in comparison to blastfurnace slags, have a
higher FeO, free lime and metallic iron fraction, resulting
in poor hydraulic properties. Due to these limitations, no
successful attempt has been reported to use steel making
slags in cement making. JSW Steel has a 0.3 milliontpa
cement plant where blastfurnace slag has long been
successfully used as an important raw material substitute.
Blastfurnace slag is a substance very closely related to
Portland cement clinker. JSW Steel procures clinker from
elsewhere. Clinker, gypsum, and blastfurnace slag are
proportioned, ground to fine powder and blended before
being sent to storage silos. In this study, blastfurnace slag is
replaced by various steel slags and is experimented with at
different proportions.

Physical requirement
Fineness (m2/kg)

Min 225

Setting time, mins

Initial

Min. 30

Final

Min. 600

Soundness

Le-chatlier, mm

Max. 10.0

Auto-clave, %

Max 0.8

Compressive strength, Mpa

3 days

Min 16.0

7 days

Min 22.0

28 days

Min 33.0

Cement specifications

Table 5. Composition design matrix


Slag mix
M1

Slag %

The composition of various steel making slags and


a comparison to iron making slag are shown in Table 1.
Free lime is considered to be one of the most undesired
components of steel slag, which hinders its usage in the
construction industry, including land filling. The presence of
free lime results in significant expansion when it combines
with water and leads to volumetric instability. A comparison
of free lime percentages in various slags is shown in Table 2.
In addition to free lime these slags also contain some
other components that are undesirable as per the standard
w.r.t final cement composition. Table 3 shows the various
desirable and undesirable components of steelmaking slags.

Clinker

Gypsum

Slag %

BF slag %

2.50

47.50

47.00

3.00

M2

5.00

45.00

47.00

3.00

M3

7.50

42.50

47.00

3.00

The Bureau of Indian Standards (BIS) has classified cement


in three different grades. The classification is mainly based
on the compressive strength of cement-sand mortar cubes
of face area 100 cm2 composed of one part cement to three
parts of standard sand by weight with a water-cement ratio
arrived at by a specified procedure. The grades are (i)
33 grade, (ii) 43 grade, (iii) 53 grade. The grade number
indicates the minimum compressive strength of cement sand
mortar in N/mm2 at 28 days, as tested by the aforementioned
procedure. The required cement specifications as per
PSCIS:455 1989 for 43 grade cement is as below (Table 4).

M4

10.00

40.00

47.00

3.00

Approach

M5

12.50

37.50

47.00

3.00

M6

15.00

35.00

47.00

3.00

M7

17.50

32.50

47.00

3.00

Each slag was dumped separately and allowed to cool.


These slags were then separately collected. Metallic iron
was removed and slags were crushed to the desired fineness.
Lab scale studies were conducted
using the slags independently at
different proportions in cement
making. Traditionally, this is done
by preparing concrete cubes,
typically 100mm x 100mm
x 100 mm then curing them
for specified times. Common
curing times are 2, 7, 28 and 90
days. The curing temperature is
typically 20 C. After reaching
the required age for testing, the
cubes are crushed in a large press.
The SI unit for concrete strength
measurement is the Mega Pascal.
The test for each variable was
repeated five times. The deviation

Figure 3. 28 day strength for various slags.

in the strength of the cubes


was well within 2Mpa, which
establishes the repeatability of the
experimental procedure.

Design of experiments
All the five different slags
generated during steel making
have been used in different
proportions in the cement mix.
Slag proportion was varied from
2.5% to 17.5%, replacing BF slag
as shown in the design matrix in
Table 5.

Figure 4. Day wise strength for 10% steel slag addition.

Results and discussion


Results of the lab scale
experiments are compared
with the properties of 100%
blastfurnace slag cement. Figure
3 shows the 28 day strength of all
the slags at different proportions
or replacement percentages with
blastfurnace slags. It is evident
that increasing the percentage of
steel slags decreases the strength.
HMDS slags have been found not
suitable to be added to cement
manufacturing even at low
proportions. LD slag, HMPT slag
and SGP slag have been found to show
comparable strengths even at 10%
replacement. However, beyond
10% only SGP slag has given the
required strength comparable
to the blastfurnace slag cement
strength.
A comparison of day wise
increase in strengths for various
slags also indicates the SGP slag to
have the best comparable values
(Figure 4).
Initial and final setting times
were found to be least for steel
slag and highest for HMPT slag
(Figure 5). However, the SGP slags
setting times are in the desired range
and close to the present cement
values.
Table 6 summarises the
chemical composition of each
mixture for 10% replacement. All
components of the SGP-replaced
slag cement matches well within
the desired values.
Though steel slag has shown
good results at lower replacement
percentage, it significantly drops in
properties at higher replacement
ratios (Figure 6). SGP slags are
still comparable at 15% and
17.5 % with the present cement
properties.

Figure 5. Setting times for 10% steel slags addition.

Figure 6. 28 day strength for higher replacements.

Figure 7. Setting times for 15% replacement.

Table 6. Chemical composition of various slag mixes


Cement

HMPT

MHDS

LD

Steel slag

SGP

Steel slag %

10.0

10.0

10.0

10.0

10.0

BF slag %

50

40.0

40.0

40.0

40.0

40.0

Gypsum %

3.0

3.0

3.0

3.0

3.0

Clinker %

47

47.0

47.0

47.0

47.0

47.0

Fe2O3

2.83 (<5)

7.4

11.9

6.1

3.6

4.6

SiO2

26.2

24.3

23.3

24.4

24.2

23.1

Al2O3

12.63

9.7

7.6

11.9

14.9

11.3

CaO

48.03

49.9

47.5

49.1

49.4

50.3

MgO

5.04

4.3

3.9

4.2

3.5

5.0

SO3

1.98 (<3)

1.9

1.8

2.2

2.4

2.8

IR

0.66

1.1

1.0

0.6

0.6

0.7

LOI

1.2

0.6

1.5

1.6

1.2

1.0

Table 7. Maximum permissible limits of various slags in cement


making
LD slag

7.5%

Steel slag

5.0%

HMDS slag

Not suitable

HMPT slag

7.5%

SGP slag

10 15%

Figure 7 shows the setting times for 15% replacement,


which is also comparable to the present cement values.
However with 15% SGP slag, Fe2O3 values increase nominally
to 6%. Here it can be concluded that under certain
conditions, SGP slag can also be tried up to 15% without
impairing the properties significantly. It is expected that
granulation generates conditions similar to the process of
ageing to the slag, which also makes the slag conducive for
usage in cement making. It was therefore recommended to
granulate the maximum amount of LD slag for its increased
recycling.

Maximum permissible limits


From the present study it is confirmed that steel slag can be
utilised in cement manufacturing in different proportions if
the different slags are used separately. Combined steel slag
may not be suitable for cement making. For individual usage,
maximum permissible limits are shown in Table 7 up to
which point it satisfies the required standards. LD slag after
granulation transforms to a form where it can be utilised up
to 15%.
To date, technology for slag granulation is applied to
blastfurnace slags only. With the introduction of a slag
granulation facility for steel slags, the JSW Vijayanagar plant
has found a unique way of utilising the steel slag in cement
making. The cement plant at JSW is presently utilising 10%
of granulated steel slag and has shown significant techno
economic and environmental benefits.

Conclusions
Slag generated from the steel making process was dumped
and is not traditionally considered usable for cement
making. With its unique layout, JSW Steel Vijayanagar plant
generates five different kinds of steel slags. These slags have
been experimented as a partial replacement of iron making

slags in cement making. LD slag after granulation has been


found to develop properties conducive to use in cement
making. 28-day strength and other important properties for
granulated LD slags have been found to be very close to the
BF slag cement strength. This has led to the development of
a new route of processing LD slag and its recycling in cement
manufacturing.

Acknowledgement
The authors express their deep gratitude to technologists at
SMS and the cement plant for their cooperation during the
project.

References
1. DIPPENAAR, R., Ironmaking and Steelmaking, 2005 Vol 32, No 1, p 35.
2. EMI, T.: Proc. 6th. Int. Conf. on Molten slags, fluxes and salts, Stockholm,
June 2000, paper 001.
3. MILLER, T.W., JIMENEZ, J., SHARAN, A. and GOLDSTEIN, D. A.: in Making,
shaping and treating of steel: Steelmaking and refining volume, 11th edn,
514; 1998, AISE Steel Foundation.
4. GOODSON, K. M., DONAGHY, N. and RUSSSEL, R. O.: Steelmaking Conf.
Proc., 481485; 1995, ISS.
5. LIU, C.-J., ZHU, Y.-X. and JIANG, M.-F.: Iron Steelmaking, 2003, 30, 3642.
6. LANKFORD, W. T., SAMWAYS, N. L., CRAVEN, R. F. and MCGANNON, H.
E. (eds.): Making, Shaping and Treating of Steel, 10th edn, 333; 1985,
Pittsburgh, PA, United States Steel.
7. MURPHY, J. N., MEADOWCROFT, T. R. and BARR, P. V.: Can. Metall.
Q.,1997, 36, 315331.
8. REEVES, B. J. and LU, W.-K.: Proc. 6th. Int. Conf. on Molten slags, fluxes
and salts, Stockholm, June 2000, paper 201.
9. MEMOLI, F., BRIONI, O., AISTech 2006 Proceedings - Volume II, p 1171
10. SHARMA, K.K., SWAROOP, S., THAKUR, D.S. Recycling of LD slag through
sinter route on direct charging in blast furnace at Bhilai Steel Plant,
Proceedings of national seminar on pollution control in steel industries;
1993. p.729
11. MASLEHUDDIN, M., ALFARABI, A.M., SHARIF, M., SHAMEEN, M.,
IBRAHIM, M., BARRY, M.S. Comparison of properties of steel slag
and crushed limestone aggregate concretes, Construct Build Mater
2003;17(2):10512.
12. OZEKI, S. Properties and usage of steel plant slag. Encosteel: steel
for sustainable development, International Iron and Steel. Stockholm,
Sweden; 1617 June 1997.
13. DAMICO, P.E., 5th European Slag Conference, Luxembourg, September
20, 2007.
14. MIHOK, P. DEMETER, D., BARICOV, K., SEILEROV, Metalurgija 45 (2006)
3, 163-168
15. OLIVEIRA DA SILVEIRA, M. et al., la revue de Mtallurgie - Cit, Oct 2004,
pp. 779 - 785.