See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/265122469

Utilisation of LD slag — An overview

Article · April 2003

CITATION READS

1 6,183

1 author:

P. N. Chaudhary
National Metallurgical Laboratory
19 PUBLICATIONS   73 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Recycling of LD Slag View project

Utilisation of LD slag as flux View project

All content following this page was uploaded by P. N. Chaudhary on 29 September 2014.

The user has requested enhancement of the downloaded file.

Journal of Metallurgy and Materials Science, Vol. 45, No. 2, April-June 2003, pp. 61-72
Printed in India, © NAIL. ISSN 0972-4257

Utilisation of LD slag — An overview

J. PAL, P.N. CHAUD NARY and M.C. GOSWAMI

National Metallurgical Laboratory, Jamshedpur - 831 007, India.

Abstract : Reuse of waste in integrated steel plants is important with regard to envi-
ronmental and economic consideration. Slag generated from basic oxygen converter
(LD-slag) is one of the recyclable wastes in integrated steel plants. This paper deals
with the present use and possible use of LD-slag. The suitability of its use in roadmaking.
metallurgical purposes and fertilizer production has been discussed. It is suitable to be
used in roadmaking due to its high hardness and cementing property, Due to its high
metallic value (Fe0-18%) and lime content (Ca0-45%), it is possible to use in BF-
ironmaking and steelmaking to replace lime and recover iron. High phosphorous con-
tent (1-3%) restricts its use in ironmaking and steelmaking. Though, a little quantity
of it is used in sinter making. the dephosphorisation is essential to improve its utilisation.
The paper gives an overview of different approaches taken worldwide by several in-
vestigators for dephosphorisation of LD slag which makes it possible to be reused in
iron and steel making. The authors draw a clear picture of worldwide research on LD-
slag recycling with some suggestions.
Key words : L,D-slag. Blending, Sintering, Dephosphorisation, Carbon reduction, Slow
cooling, Di-calcium silicate, Fertilizer making, Recycling in innonaking.

INTRODUCTION

Integrated steel plants generate many types of wastes at different stages of processing. These
wastes have adverse effects on the environment. Utilisation of waste is an environment friendly
cost saving technique. Raw materials constitute a major portion of production cost. there-
fore, if wastes can be used as substitute of raw materials, conservation of natural resources is
possible with lowering of environmental hazards simultaneously.

Slag generated during steelmaking in basic oxygen converter (LD-Converter) is one of the
important waste materials in an integrated steel plant. Generation rate of LD-slag is 150-
180kg per ton of crude steel. In Indian condition". Total generation per annum is 0.98 mil-
lion tonne''' in Tata Steel, about 1.28 million tonne" in SAIL and world wide generation is
about 47 million tonne per annumol. The slag contains various desirable substances like
CaO. Fe and Mn. The chemical analysis of several phases is summarized in Table I . CaO is
an important oxide present in the slag which can be utilised in other metallurgical processes
as flux material instead of lime or lime stone. High quality steel products require extremely
low phosphorous contents to avoid its adverse effect on mechanical properties due to segre-
gation in grain boundaries during solidification and heat treatment. The phosphorous con-
tent of BOF or LD slag is too high to be reused in ironmaking and steelmaking. In ironmaking
cent percent phosphorous go to the metal phase and thus in steelmaking phosphorous load of
slag increases.

Blast furnace slag has a long-term market in cement fertilizer and construction industries,
whereas. LD-Slag is not suitable due to its high phosphorous content. Only 40-50% of LD-
Slag recycling is possible in India till date's'. If removal of phosphorous is possible. this

61
 J. PAL, P.N. CHAUDHARY and M.C. GOSWAMI

Table I Composition of several phases in LD slagm

l 1
Composition (wt%)
Mineral Ca0 SiO, Fe0 Mn Mg0 P,O, A1,0 TiO, Cr,O,
phase
Di-calcium 58.00 33.84 0.54 - 0.01 3.62 0.67 0.50 0.04
silicate
Tricalcium 68.20 25.70 2.15 1.55 0.08 1.10 0.30 0.37 -
silicate
Dicalcium 49.64 1.48 48.11 0.36 4.24 0.02 - - -
ferrite
Dicalcium 52.70 2.55 33.31 0.88 0.43 0.32 3.25 8.53 0.39
ferrite
Titanate
Magnesio 2.12 2.08 61.80 17.50 5.68 - - - -
Wustite
.,

Slag recycling is possible in India till date]. If removal of phosphorous is possible, this
LD-slag can be recycled in steelmaking as a flux material and also can be charged in blast
furnace in place of lime stone. Use of this slag not only replace lime but also avoids heat loss
for calcination of limestone. Removal of phosphorous, therefore, will allow the use of LD-
slag by reducing not only the direct steelmaking cost, but also the disposal cost of the slag.

Present Uses of LD-slag

LD slag bolder is used in road making and floor preparation for its high hardness and ce-
menting property. In Durgapur Steel Plant a major portion of the LD-slag is sold in the form
of bolders for roadmaking. Similarly all the steel plants in India are selling more than 50%
LD slag for road making and ground filling. Tata Steel's LD- slag has been proved to be an
excellent railway ballast material and, as such, is being used by Indian Railways. The lime
and magnesia present in LD-slag absorb moisture and CO, from atmosphere to form hydrox-
ides and carbonates respectively which lead to the volume expansion or swelling resulting in
crack formation in road and building materials. This problem can be overcome by weather-
ing the slag for six to nine months for hydration of free lime before the slag is used'''.

LD-slag is used as cement making for replacement of clinker. Although LD-slag usage in
cement making is commercialised in China, Indian cement manufacturers are still unwilling
to take advantage of the low cost raw material for cement manufacture'''. LD-slag has higher
CaO content in comparison to BF-slag, which acts as an activator and gives better strength.
However, presence of P,05 results in corrosion of reinforced materials in concrete structure.
If only 10% LD-slag is used in cement, the P,O, content will be around 0.3% which is not so
harmful in portland slag cement (PSC), because low P,05 in PSC react; with alkali in slag
contributing little strength of cement'''. Therefore, more than 10% LD-slag use in PSC is not
possible. Iron oxide present in LD-slag forms a phase, tetra calcium alumino ferrite (C4AF)
which has an adverse effect on the quality of cement'''. The total iron oxide content should
not be 5%. The ferrugeneous portion of LD-slag can be separated by magnetic separation
technique. However, for magnetic separation, crushing and grinding are required which are
very costly. At Tata Steel, a project has been initiated in collaboration with Lafarge India to

62 J. MET. MATER SC., Vol. 45 No. 2, 2003

 UTILISATION OF LD SLAG — AN OVERVIEW

Table 2 : Results of bench scale trials of steel slag cement's'

,
"No. Composition of mix• Strength (Mpa ) after
3 days 7 days 20 days
1. 15% LD-slag 85% ,clinker and gypsum 31.7 41.6 61.1
2. 20% LD-slag 80% ,clinker and gypsum 27.3 40.0 60.5
3. 25% LD-slag 75% ,clinker and gypsum 24.8 38.6 58.7
4. 40% BF-slag + 15% LD-slag + clinker 24.1 40.1 59.4
and gypsum
make a use of LD-slag in cement making'51. The bench scale trial is being conducted at the
Jojobera Cement Plant of Lafarge. The results of the bench scale trial are summarized in
Table 2, which are very promising to the quality of cement. After crushing and grinding to
suitable size LD-slag is used as a flux material in sinter making. Tata Steel uses up to 50% of
LD slag in their sinter plant and Steel Authority of India Ltd. (SAIL) uses up to 36.6%t61 of
the same.

LD-slag is harder to crush compared to lime stone and therefore, it may be difficult to attain
the desired fines. At Tata Steel the two staged crushing facility at the raw materials bedding
yard has been found to be adequate to crush it to the desired size (90% to —3mm) for sinter
makingt9).

LD-slag does not demand heat for calcination when used in sintering. It contains a substan-
tial amount of calcium silicates. Pure di-calcium silicates are high melting compounds (2403K)
and so are the solid solutions rich in calcium silicates. This temperature is not attained within
a sintered bed. However the presence of iron oxide environment around calcium silicates
prevailing in a sinter bed changes the situation. A mixture of 23% di-calcium silicate
(2CaOSiO,) and 77% FeO would melt at around 1553K only. Similarly, the lime rich phases
having melting ranges over 2273K, when adequately mixed with iron oxides can have liquidus
temperatures of the order of 1473K. Microstructural observation of laboratory sinter and
plant sinter were taken up and found that characteristic microstructural feature of LD-slag
could not be detected in any of these samples. Therefore, it can be said that for all practical
purposes, LD-slag got completely assimilated during the sintering. Incorporation of LD-slag
has not been found to affect the quality and properties of sinter in terms of size, strength and
RBI even up to 40kg per ton of sinter. Excise duty imposed on LD-slag by the Govt. of India
restricts its use in railway ballast, cement making. small-scale industries like foundries and
electric arc furnaces.

RECYCLING OF LD-SLAG

LD-slag may be used in refining of steel or in ironmaking due to its high metal value and
lime content. It may also be used as a fertilizer due to its high phosphorous content. Pres-
ently it is neither used in steel melting and iron making nor in fertilizer making. To use this
slag in melting or in iron making, dephosphorisation is required, whereas, to use it in fertil-
izer making, high phosphorus contents are required. In this age of competitiveness to minimise
production cost, a good step can be taken to reuse LD-slag in steelmaking and ironmaking
process. The phosphorus content of the blast furnace usually ranges from 0.1 to 0.3 % de-
pending upon the type of burden used, whereas the bulk of quality steels must have phospho-
rus level below 0.02%. Thus almost 90% phosphorus present in the hot metal is removed as

J. MET. MATER SC., Vol. 45 No. 2, 2003 63

 J. PAL, P.N. CHAUDHARY and M.C. GOSWAMI

Table 3 : Calculated values of P increase in hotmetal due to

recycling of LD-slag (P205 = 4%)
P2 0_ in slag Amount of recycling, Increase of P load in hot metal P in hot
(kg/ton of hot metal) due to recycling, (Kg/ton of metal, %
hot metal)
4% 0 0 0.2
(without 50 0.87 0.29
dephosphorisation) 100 1.74 0.37
150 2.60 0.46
2% 50 0.43 0.24
(After 50% 100 0.87 0.29
dephosphorisation) 150 1.31 0.33

and magnesia which can easily substitute almost equal amount of limestone in the Blast
furnace burden provided phosphorus is removed from the slag. However, the phosphorus
content of hot metal will increase from the existing level as shown in Table 3, if phosphorus
is present in the recycled slag. This will require additional consumption of flux at later stage.
Therefore, steelmaking slag for recycling must have low (<.0.01%) phosphorus. An alter-
nate approach for producing low-P(<.0.01%) steelmaking (BOF) slag could be pretreatment
of hot metal before it is sent to converter. The removal of phosphorus from hot metal is
much easier due to its relatively lower temperatures (1573-1623K) compared to the removal
in BOF where high temperatures (1873-1993K) prevail. However, intensive desiliconization
of the hot metal is a prerequisite for an effective dephosphorization. Therefore, removal of
phosphorus from Steelmaking slag is a better option to make it recyclable to Ironmaking
processes. Several attempts for the dephosphorisationD"-12-15-"I have been made to address
this problem which are summarized below:

Physical Process

Different authors have gone through physical processes like magnetic separation, floatation,
dual phase separation etc. Magnetic separation is used by H. Suito et. Am. Particles with
high magnetic susceptibility will be separated by a light magnetic field and weaker magnetic
particles will be separated by a strong magnetic field. Therefore, the heterogeneous mag-
netic field of different intensities can separate different particles. However, this is not a very
effective way of dephosphorisation.

Dephosphorisation can be done by electrolytic means. Slag is treated as an electrolyte and a

suitable voltage in electrode can separate different ionic species as deposit / precipitate I gas.
This is not an economically viable process. Phosphorous can also be removed by flotation
techniques. Air is passed through the suspension of fine sized slag powder in water. Hydro-
phobic particles adhere to the air bubble and form froth at the top of the pulp. This froth is
skimmed off and thereby some phosphorous can be removed. This technique is also not
suitable for industrial application.

Dual liquid phase separation methods also have been used to separate phosphorous from
slag. All the methods of P removal, mentioned above, involve some basic difficulties in
practical.application. Problems may be encountered during up-scaling and techno-economic
feasibility.

64 J. MET. MATER SC., Vol. 45 No. 2, 2003

 -UTILISATION OF LD SLAG AN OVERVIEW

Table 4 : Equilibrium temperatures for reduction of different oxides in slag by carbon

Metal oxide Equilibrium temp, 1T‘
Fe2O3 970
Fe0 1124
P205 1443
Si02 1950
Mn0 1987
Ca0 3362

Chemical Process

Pyrometallurgical treatment of LD-slag was done by different investigators. Shiomi et. Ai" )
proposed a method in which phosphorous is removed through evaporation by adding silicon
to a Fe-P-C alloy obtained as a result of reduction of slag with carbon.

During reduction of converter slag in an electric furnace it is possible to form two different
phases: one metallic and other nonmetallic:0'i. Slag powder is properly mixed with graphite
powder and melted in an electric arc furnace. The less stable oxides like Fe,0,, FeO and P,05
are reduced and form a metallic phase. On the other hand, the concentration of CaO, Mg0
and Si02 increases and nonmetallic phases are formed. In thermodynamic calculation (Table
4), the equilibrium temperatures indicate that only Fe,03, Fe0 and P,05 can be reduced by
carbon at the temperature range of 970 to 1443K. Whereas, the equilibrium temperature of
CaO, MnO, Si02, A1,0, and TiO, are much higher. As P,05 in slag is present in the form of
3CaO.P,05, the reduction of it is not possible at 1443K as AG value is very high (AG =
141690 cal at 1400K)". The overall reaction can be represented by.

3CaO.P,05 + 5C + 3SiO, = 3(CaO.SiO,) + 5C0 + P,

-40
The equilibrium pressure of furnace gas for the above reaction reaches latm at about 1423K.
However, this reaction requires a temperature above 1773K to accomplish a good separa-
tion". The compositions of metallic and nonmetallic phases are shown in Tables 5 and 6
respectively, total 13 experiments have been conducted with gradual increase in the propor-
tion of carbon in the melt from experiment 1 to 13. Composition of nonmetallic phase can be
adjusted to produce Portland clinker by adding 5-6% CaO. It can be used as a raw material in
Ca-Mg fertilizer industries also. The metallic phase can be used in metallurgical industries.

Reduction of CaO-SiO,A1,0,-Fe0 slags by solid carbonaceous materials such as

graphite, coke and coal char was investigated at reaction temperatures of 1673K to 1723K
by Sarma B. et. a/.1151. They used stationary and rotating carbon rods in a slag melt, stationary

Table 5 : Chemical composition of metallic phases, wiovni

'Melt C Fe Si Mn Cr S
1-3 0.75 97.74 0.01 0.98 0.16 0.28 0.015
4-6 0.86 96.70 0.03 1.61 0.21 0.46 0.018
7-9 0.93 94.37 0.04 3.06 0.42 1.04 0.019
10-12 1.08 92.07 0.65 3.84 0.41 1.49 0.026
13 0.92 91.34 0.75 5.40 0.11 1.40 0.028

J. MET. MATER SC., Vol. 45 No. 2, 2003 65

 J. PAL, P.N. CHAUDHARY and M.C. GOSWAMI

Table 6 : Chemical composition of nonmetallic phases, wt%1121

'Melt C Ca0 SiO, Mn0 Mg0 Fe0 A1203 P205

1-3 0.15 57.63 21.68 5.53 5.94 4.92 1.31 1.31 0.15
4-6 0.21 58.74 23.76 5.28 5.61 4.20 1.61 1.18 0.12
7-9 0.27 61.50 23.21 4.13 5,19 2.91 1.40 0.83 0.12
10-12 0.26 62.74 23.75 2.99 4.49 2.82 1.49 0.32 0.12
13 0.46 62.14 26.78 0.83 6.75 0.93 1.64 0.12 0.17
Con- 44.50 16.63 5.40 5.26 18.1 1.68 1.24 0.11
verter
Slag

and horizontal carbon surface and pinned stationary spheres as the reductants. They found
that
' i. Reaction rate increased with increase of slag Fe0 content. However, this variation was
not linear with FeO content
ii. The reaction rate also increased with increase in rotation speed of carbon rod at given
Fe0 content of slag.
iii. A small increase in reduction at given Fe0 content was found when horizontal coke
surface and coke spheres were used as reductant instead of graphite and coal char.

Molten slag has sufficient thermal energy to reduce the oxides in the slag by using coal or
coke without much addition of energy for endothermic reaction as follows

MX° + C tS ) --xM + CO(v) 2

Reduction of BOF slag has been studied in a reactor composed of two chambers as shown in
Fig. 111"1. Here molten slag, just after tapping is charged into first chamber where carbon
powder is mixed. The Fe0 and Mn0 are reduced in the first reaction chamber, but little
phosphorous is reduced. Then, the slag flows into the second reaction chamber where phos-
phorus in the slag is reduced as per reaction,

Flux bins CaO,CaF2, Coal

Gas Cleaner

BOF slag .:0;\

Reduction
Furnace

Chamber-1 Chamber-2A
Hot metal

Tundish

Hot metal pretreatment

station

Fig. 1 : Schematic of BOF slag reduction process.

66 J. MET. MATER SC., Vol. 45 No. 2, 2003

 UTILISATION OF LD SLAG — AN OVERVIEW

(P02.5), + 2.5Cs = 0.5P2to + 2.5C0(v) 3

The electrical energy can be used to compensate the endothermic heat of reactions.

The possibility of reducing BOF slag was done by Ono, H et. al.1'71. 5kg of BOF slag was
melted under Ar atmosphere and the temperature was raised to 1873K. After attaining the
desired temperature, Al, Al-dross or coal was added to the slag as a reducing agent. The
sequence of reduction of oxide had been determined. FeO was reduced before any other
oxides. and then, the stable oxides, MnO and P205 began to be reduced and phosphorus gas
phaSe was generated. 50-60% of the phosphorus initially present in the BOF slag could be
vaporised and most of the remainder would be dissolved in the reduced metal.

Guo and Wane) studied the reduction of phosphorus in molten slag containing 8.3% A1203
and 3.5% P,O, with basicity of CaO/Si02 = 1.1 at 1735K, 1823K and 1893K. The experi-
mental results showed that the temperature had an effect on the reduction of phosphate by
graphite. They also investigated the possibility of the reduction of phosphorus by CO gas at
temperature 1823K. The reduction rate increased with increasing CO gas flow rate. They
concluded that the reaction rate of P,O, was not controlled by diffusion of P2 gas phase
product, and the rate was most likely controlled by chemical reaction.

The kinetics of phosphorus reduction in slag was more thoroughly studied by Ryil, J.Y et.al.".
Reaction-3 is a three-phase reaction (molten slag, solid carbon and gas). They proposed a
phosphorus reduction mechanism at the slag-solid interface as shown in Fig. 2. After reduc-
tion reaction-2 was initiated, a gas film separated the molten slag from solid carbon. Reac-
tion-3 then proceeded with the aid of gaseous intermediates (CO + CO2 ) via gas-slag and
gas-carbon reaction as follows.

P02 , + 2.5C0‘o = 0.5P2(0 + 2.5CO2(9) 4

CO,{_) C),) = 2C019i 5

The reduction reaction-4 occurred at the gas-slag interface and reaction-5 takes place at the
gas slag interface as per following.steps.

(P02 5)
Slag Phase
(P02.5)+ 2.500(9) = 0.5P2(9) . 2.5002(9)

( CO

Gas
Phase CO2 + C = 2C0

Fig. 2 : Schematic of reduction of P205 in BOF slag by solid carbon.

J. MET. MATER SC., Vol. 45 No. 2, 2003 67

-

J. PAL, P.N. CHAUDHARY and M.C. GOSWAMI

- Diffusion of PO, ; from the bulk of the slag to the slag-gas interface.
- Chemical reaction at the slag gas interface, i.e., reaction-4.
- Diffusion of CO, away from the slag-gas interface towards the gas carbon interface and
P, away from the slag.
- Chemical reaction at the gas-carbon interface, i.e., reaction-5.
Diffusion of CO away from the gas carbon interface towards the slag-gas interface.

At higher temperatures the chemical reactions 4 and 5 were faster, therefore, liquid phase
mass transfer of PO,.; in slag was assumed to be the primary rate controlling, step at low
concentration of phosphorus in slag.

Physico Chemical Process

Different investieators12{-"1 have done analysis of different phases present in slag. All of
them have found three major phases like di-calcium silicate, di-calcium ferrite and Mg-Mn
wustite. Analysis of different phases present in LD-slag is shown in Table I. Almost 90%
phosphorous of the slag bath comes to the di-calcium silicate phase, because the solid solu-
bility of P,O, in di-calcium silicate is 10%. Therefore, the main idea is to separate di- cal-
cium silicate phase from the slag bath. Amongst all the phases, di-calcium silicate is the
lighter phase. While, the solidus temperature of this phase is higher than other phases. There-
fore, during solidification of the slag, nucleation of this phase occurs earlier than other phases.
Due to its lightness, the erains float upwards of the bulk. Therefore, if the LD slag is super-
heated up to 1923K in a crucible and then allowed to cool down slowly, separate phases will
be formed. The different phases can be identified by observation under microscope or through
Electron Probe Micro Analyser (EPMA). Cooling rate should be controlled at higher tem-
perature range and normal cooling at lower temperature range.

LD-converter slag produced in a 170-t LD-converter at Nippon Steel's Sakai works42"iunder

various blowing conditions were used for the experiments. Samples were prepared by crush-
ing 10kg of lump slag to below 3mm pulverising to less than 100mesh. Different compo-
nents of samples were estimated by fluorescent X-ray analysis. The slag has been super-
heated to 1923K and slowly cooled to lower temperature then at room temperature, the
mineral phases were identified by microscopic and EPMA examination. As a result of slow
cooling, CaO, SiO, and P,O; are enriched in top and FeO, Fe.,0, and Mn0 in bottom. Analy-
sis of top and bottom layer of slag is shown in Table 7. They came to the conclusion that di-
calcium silicate is apt to separate more efficiently with higher total iron content in slag and at
higher start temperature of cooling, close to liquidus temperature. The efficiency of separa-
tion can be improved by blowing oxygen into the molten slag before cooling.

Fujita et.a1.1211 had done an experiment for dephosphorisation of BOF slag. The as-received
slag samples were ground to 1.65mm and 200gm of sample was placed in a magnesia cru-
cible and heated to its fusion temperature of 1643K in a Lindbergh box furnace, held at this
temperature for one hour and then slow cooled at cooling rate of 1, 0.5, 0.2 and 0.1"K /min.

Table 7 : Composition of top and bottom layer of slagu."1

Fet Ca0 SiO, Mn0 Mg0 P20.5

Top 14.0 47.6 18.5 3.0 4.1 3.14
Bottom 29.2 34.9 7.1 5.9 5.6 0.96

68 J. MET. MATER SC., Vol. 45 No. 2, 2003

 UTILISATION OF LD SLAG – AN OVERVIEW

Table 8 : EDS analysis of mineral phases''''

(
Fet Fe0 Fe2O3 Ca0 SiO, Mn0 P20, Mg0 AL,O, Wt670-
Dicalcium 3.62 4.62 — 66.07 21.70 1.68 4.17 0.01 1.34 43
Silicate
Di-calcium 24.30 – 34.74 48.76 0.67 6.97 0.75 0.36 4.89 29
Ferrite
Wustite 33.73 43.39 – 2.56 0.00 26.27 0.13 25.75 0.08 28

The microstructure of the as received and slow cooled slags were examined under a scanning
electron microscope and the major phases were analysed by Electron Diffraction Spectrum
(EDS). The mineralogical compositions were determined by X-ray diffraction. The slow
cooled slag samples were ground to –90mm and separated in a Sala high gradient magnetic
separator. From the X-ray diffraction analysis three phases- wustite, dicalcium ferrite and
dicalcium silicate were identified. Much of the manganese and magnesium were in the wustite
phase whereas phosphorous was mainly in the di-calcium silicate phase. Di-calcium silicate
was the predominant phase, amounting to about 43% by weight whereas the wustite and
dicalcium ferrite phase were about 28% and 29% respectively as shown in Table 8. From
Table 8, it is apparent that much of iron and manganese are in the wustite and dicalcium
ferrite phase, whereas phosphorous and silica are in the di-calcium silicate phase. The sepa-
ration of different phases in slag is dependent on conditions which are summarised as fol-
lows :-

Composition

After formation of di-calcium silicate crystals during solidification it moves towards the top
of the bulk through the rest of the liquid. If the fluidity of liquid phase is higher, movement
of di-calcium silicate crystals is easier. Therefore, separation is more clear. The fluidity of
slag and amount of seperation at a particular temperature depends mainly on the composi-
tion of slag,. Therefore, amount of separation decreases upon composition as follows :-
i. If FeO content of slag is very low, fluidity of slag decreases and hence separation de-
creases.
ii. If CaO/ SiO., ratio is high, the fluidity of slag further decreases
iii. If high dolomite is used to prolong the lining life of a converter, magnesio-wustite
becomes primary crystal, because, MgO becomes high. Therefore, the rate of phospho-
rous separation decreases.

Starting Temperature of' Slag

If the starting temperature of cooling is higher, the separation ratio of P,O i is higher. The
difference between liquidus temperature and starting temperature of crystallization will be
about 100K minimum1201.

Cooling Rate

Floating speed of di-calcium silicate particles is affected by particle size. The growth of
particles is accelerated as cooling rate decreases. Therefore separation rate of dicalcium
silicate increases with decrease in cooling rate. Separation is done effectively at cooling rate
below 2"K/min12 1.

J. MET. MATER SC., Vol. 45 No. 2, 2003 69

 J. PAL, P.N. CHAUDHARY and M.C. GOSWAMI

Blowing Oxygen

Suspended Fe and Fe0 oxidise to higher oxides like FeO, and Fe,03. As the oxidation reac-
tion is exothermic, the slag temperature increases. Fe0 and Fe,03 have lower melting points
in comparison to metallic Fe. Therefore, the melting point of slag decreases and hence fluid-
ity increases. Thus oxygen blowing can increase both rate and degree of separation of P,05
from slag.

Addition of Fluorspar

Addition of flourspar to the slag can improve grain growth''-'-1. It has been seen that the
addition of 4% fluorspar is suitable to promote grain grOwth and hence improves rate of
separation of P,05. However, flourspar causes severe erosion of refractory linining and de-
creases the lining life.

Use of Slag in Fertilizer Industries

In India the efforts have been made in Tata Steel to use this slag as a soil conditioner in the
paddy fields, tea gardens etc. after grinding the same to 300 mesh'51. NKK in Japan''-'' has
recently developed a unique process to produce eco-friendly slow release potassium silicate
fertilizer from the slag, which is generated during the desiliconisation process of hot metal at
the steel mill;NKK's idea is based upon making use of slag's ingredients, which work effec-
tively on plant. In this process, potassium carbonate (K,CO3) pellets are added to the molten
slag, containing silicon dioxide (SiO,) as its main ingredient, in the hot metal ladle and
melted uniformly at 1673K. The molten mixture is collected from the ladle, then cooled and
pulvarised into granular fertilizer. The formed fertilizer, which is blackish gray in colour,
comprises of vitric potassium silicate as its main ingredient and exhibits slower-release ef-
fects than conventional quick-acting chemical fertilizer such as potassium chloride, potas-
sium sulphate and urea. It is absorbed slowly by the weak citric acid produced in the root of
farm products and remains there for a lengthy period of time. The new potash fertiliser is a
highly eco-friendly product, since it is nearly insoluble in water and it does not easily pollute
river or ground water. It contains no elements that acidify soil and concentrate salt. It is
produced from by-product slag without applying extra heat in the melting process, thus
conserving energy and resources.

NKK has succeeded in developing eco-friendly large marine blocks, which are designed for
use as artificial reefs for living marine•organisms. NKK's Mayine Block is a large carbonic
solid (CaCO3) produced by blowing carbon dioxide in to pulvArised and moisture controlled
slag compacts which principally consist of lime (Ca0), in the mould. By absorbing CO„
carbonated solid blocks help reduce CO, emissions and alleviate global warming, while
stabilising preferably in sea water as marine plant cultivating beds. Since April, 1999, NKK
has been conducting demonstration tests of its marine blocks (1m31m 350cm weighing
about 1 ton) on the sea bed 5m below the surface in western Japan.

SUGGESTED METHODOLOGY FOR RE-USE

After tapping of the heat the slag can be treated under the slow cooling process as mentioned
above. The three phases (di- calcium silicate, dicalci um ferrite and wustite) can be separated
as shown in the flow chart, given below. After separation, iron rich portion (wustute) can be
recycled to ironmaking or steelmaking and lime rich portion (di-calcium ferrite) can be

70 J. MET. MATER SC., Vol. 45 No. 2, 2003

 UTILISATION OF LD SLAG — AN OVERVIEW

FLOWCHART

LD- SLAG
Fe0-12.8%, Mn0-6.9%
Mg0-9.6%
P205-2.6%, Ca0-38.9%
Si02-9.8%, A1203-2.6%

DICALCIUM SILICATE DICALCIUM FERRIT WUSTITE

2CaO, Si0,-3CaO, P20, 2CaO—Fe2O3 Mg0—MnO—Fe0
30-40 wt% 30-35 wt% 25-3.0 wt%
P20,-4.17% P20,-0.75% P20,-0.13%

SEPARATE DIRECTLY USE Add metallic iron Dicalcium-

PHOSPHOROUS FOR SOIL powder some coke Ferrite reduced
CONDITIONER bridge during to Mg-Mn-
slow cooling Wustite

If P is within tolerable limit

v
USE RECYCLE Ca0 RECYCLE FOR
PHOSPHOROUS TO FOR IRON & IRON & STEEL
MAKE FERTILISER STEEL MAKING MAKING

converted to Mg-Mn-wustite by adding a mixture of metallic powder and coke bridge. If

P-content is within tolerable limit in di-calcium ferrite, it can be used directly in ironmaking
and steelmaking. On the other hand P-rich portion (di-calcium silicate) can be used for fer-
tilizer making.

CONCLUSION

LD slag is one of the important waste materials generated in steel plants. Besides its use as
road making and cement producing, it can very well replace lime addition to the steelmaking
route due to its high lime content. However, the presence of phosphorous in it is quite high
which restricts its utilisation in iron and steelmaking. The amount of phosphorous can, how-
ever, be reduced by physical and chemical means. Controlled cooling of molten slag can
separate the various phases including the lighter phase of di-calcium silicate that consists of
P,O, phase, as the solid solubility of P,05 in di-calcium silicate is quite high. The phospho-
rous enriched phase can be effectively used as a fertilizer whereas the phase enriched with
CaO and FeO can be recycled back to the iron and steelmaking processes. As an alternative
to the dephosphorisation of LD-slag, external desiliconisation followed by dephosphorisation
can reduce silicon and phosphorus load in hot metal and hence the phosphorus content in
final steelmaking slag gets reduced. However, external desiliconisation and dcpohos-
phorisation consume fluxes and produce high phosphorus slag which again needs to be dis-
posed off. Therefore, recycling of LD-slag on removal of P seems to be a better approach.

REFERANCES
1. Yadav, U.S., Das, B.K., Kumar, A and Sandhu, H.S., (2002), Solid waste recycling through

J. MET. MATER SC., Vol. 45 No. 2, 2003 71

 J. PAL, P.N. CHAUDHARY and M.C. GOSWAMI

sinter status at Tata Steel, Proc. of Environment and Waste Management, NML, Jamshedpur,
India, pp. 81-94.
Basu, G.S., Sarker. P.K., Sharma R.P and Dhillon, A.S.. (1997), Recycling and reuse of solid
waste at Tata Steel, Tata Search, pp. 118-120.
3. Basu, P., (2002). Alternative ironmaking technologies: an environmental impact analysis. Pro-
ceedings of Environment and Waste Management, NML, Jamshedpur, India, pp. 194-202.
4. Takano, Cyro., et. al., (2001). Recycling of Solid Waste From Integrated Steel Plant: A Sustain-
able Alternative. Materials Transactions. 42(12), pp. 2560-2570.
5. Basu, G.S., Sharma, R.P and Dhilon. A.S.. (2002). Solid waste management in steel plants-
challenges and opportunities, Tata Search. pp. 39-42.
6. Mukhedee, A.K and Chakraborty, T.K., (2000), Towards zero waste concept and possibilities in
Indian iron and steel industry, Proceedings of Environment and Waste Management, NML,
Jamshedpur, India, pp. 37-49.
7. Sharma, R.P., Basu. G.S., Maheshawari, M.D., Tibdewal, P.K and Piplai, K.C.. (2003), Utilisation
of LD-slag in cementmaking- experience at Tata Seel. Proceedings of ASIA Steel International
Con ferance, Jamshedpur. India. pp. 1.i.7.1-1.i.7.7.
8. Banerjee, H.N., (1980), The technology of portland cement and blended cement, A.H. Wheeler
and Co. (1st eds), Bengalore. pp. 8-15.
9. Roy, T.K., Sinha, B.B., Singh, B and Das, A.K., (1998), The metallurgy of solid waste recycling
in integrated steel plant, Tata Search, pp. 123-126.
10. Suito, H.. Hayashida. Y and Takahashi, Y., (1977). Minaralogical study of LD converter slags,
Tetsu-to-Hagane, 63(8), pp. 1252-1259.
11. Shiomi, S., Sano, N and Matsushita, Y.. (1977), Removal of phosphorus in BOF slag. Tetsu-to-
Hagane, 63(9), pp. 1520-1528.
P. Dziarmagowski. M., Karboniczek, M., Pyzalsky, M and Okon, J., (1992), Reduction of con-
verter slag in electric arc furnace. Ironmaking and Steelmaking. 19(1). pp. 45-49.
13. Peck, D.R.. (1971). The preparation of phosphorus. Suppliment to Mellor's comprehensive trea-
tise on inorganic and theoritical chemistry, V11(11I) ( Phosphorus) Wiley- Interscience.
14. Elliot, J.F., Gleiser, and Ramakrishna, V.. (1963), Thermochemistry for steelmaking. 2. Addision-
Wisley, p. 303
15. Sarnia, B., Cramb, A.W and Fruehan, R.J.. (1996), Reduction of FeO in smelting slag by solid
carbon: experimental results. Metallurgical and Materials Transactions. 27B(5), pp. 717-730.
16. Ryu, J.Y.. Heo, W.O., Yoo, B.D.. et.al., (1995), POSCO Technical Paper.
17. Ono, H., lnagaki, A., Masui, T., Narita. H., Mitsuo. T., Nosaka, S and Gohda, S., (1980), Re-
moval of phosphorus from LD converter slag by floating of di-calcium silicate during solidifica-
tion, Tetsu-to-Hugane, 66(9). pp. 1317-1326.
18. Guo, Z., Wang. D and Xu, Z., (1994), Fundamental research on phosphorus removal in the
smelting reduction process. Steel Research, 65(2), pp. 47-52.
19. Ryu, J.Y. Fruhan, R.J and Morales A.T., (1999), Kinetics of phosphorus vaporisation from slag.
Iron and Steelmaker. January, pp. 59-68
20. Ono. Hitoshi.. Inagaki. A., Masui, T., Narita. H., Nosaka, S.. Mitsuo, T.and Godha, S., (1981).
Transactions-ISIJ, 21(2). pp. 135-144.
21. Fujita, T and Iwasaki, I., (1988), Phosphorus removal in high gradient magnetic separation from
steelmaking slags slow cooled in an air atmosphere. Process Mineralogy VII , Minerals, Metals
and Materials Society, pp. 293-308.
21. Fregeau, E. Wu., et. al., (1990), In-situ grain size determination of slow cooled steelmaking
slags. Process Mineralogy IX , Minerals, Metals and Materials Society, pp. 429-439.
23. NKK-promoting effective utilisation of steel making slag, NKK Monthly, 2000. December. 25.

72 J. MET. MATER SC., Vol. 45 No. 2, 2003

View publication stats