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Thesis Slag Desulphurisation
Thesis Slag Desulphurisation
Thesis Slag Desulphurisation
MASTER'S THESIS
Supervisors
Professor Bo Bjrkman(LTU)
Sven-Olof Ericsson(OVAKO)
Lule University of Technology
Master Thesis in Minerals and Metallurgical Engineering
Department of Chemical Engineering and Geosciences
Division of Process Metallurgy
ABSTRACT
The cleanliness of steel with respect to non-metallic inclusions and the precise alloy
compositions in the steel products have always been of great concern in steel making
technology. The development of steel making process to meet the compositional requirements
for specific mechanical properties such as ductility, toughness, fatigue and machinability
requires dynamic and continuous investigations.
The refining of molten steel in the ladle furnace to meet the required compositional range
requires the optimisation of the process parameters. For sulphur removal control, parameters
such as argon gas flow rate through the porous plugs, inductive stirring effect, vacuum
pressure of the tank degasser, amount & composition of the top slag should be optimised. In
this thesis project an investigation was carried out on the factors that influence the top slag
composition before vacuum treatment and also to optimise the top slag composition for
precise sulphur removal. 12 heats were followed during the project; slag samples, steel
samples, temperature and oxygen activities were taken at eight different process stages at
Ovako steel mill. A relatively large variation was observed for all the oxide components of
the slag phase before vacuum treatment in all the heats followed. A PLS analysis made shows
that topslag composition before degassing is influenced by the amount of slag former added,
oxygen potential at tapping, the yield of Al and Si deoxidants into the steel at tapping. The
model has a poor predictability because some important parameters such as ladle glaze
condition, amount of EAF slag tapped and refractory wear could not be measured.
An alternative solution of extra slag practice was suggested instead of modelling the
composition and mass of carry over slag left after slag removal. The extra slag practice
involves the addition of lime during tapping so as to aid the removal of all the slag before
ladle refining and thus optimisation of the new synthetic slag for precise sulphur removal
could be easily achieved.
Finally the investigation of the desulphurisation process shows that degassing time, argon gas
flow rate through the porous plugs are as well important as the slag mass and composition in
order to achieve a precise sulphur removal.
ii
ACKNOWLEDGEMENT
I am eternally grateful to my creator and my saviour whose mercy and love has been without
limit in my life. To him who gave this opportunity, His mercy endures forever
I want to appreciate Swedish institute (S.I), who has granted me the scholarship to study in
LTU. My profound gratitude goes to my supervisor at Ovako Steel AB, Sven-Olof Ericsson
for accepting me to carry out this research work under his supervision and also for sharing his
rich experience with me during the course of the work. I appreciate my supervisor in LTU
Professor Bo Bjrkman for his contribution in this project work and his pedagogic style of
knowledge transfer in the classroom. I also like to appreciate the technical support of Jan-Eric
Andersson, Robert Eriksson, Patrik Undvall, Slve Hagman, Lars-Erik Borgstrm, Ove
Grelsson, Rolf Nilsson and all the team members working at the EAF and Ladle furnace at
Ovako Steel AB Hofors. I also appreciate the moral support of the members of Pingst Kyrkan,
Hofors during my stay and all my friends in Lule.
This will be incomplete if i dont appreciate my dearly beloved Abiola, who has been a good
companion for me. My parents Mr and Mrs I. B Famurewa you are part of what I am today.
This could not have been, without the support of my wonderful brothers, Sunday and Festus.
I am grateful unto you all.
iii
TABLE OF CONTENTS
ABSTRACT .............................................................................................................................. ii
ACKNOWLEDGEMENT ...................................................................................................... iii
TABLE OF CONTENTS ........................................................................................................ iv
1.0 INTRODUCTION .............................................................................................................. 1
1.1 Background ...................................................................................................................... 1
1.2 Historical Background of Ovako...................................................................................... 2
1.3 Process Description at Ovako Steel AB Hofors ............................................................... 3
1.4 Effects of Sulphur on Steel............................................................................................... 4
1.5 Aim of the Project ............................................................................................................ 4
2.0 LITERATUTRE REVIEW ............................................................................................... 6
2.1 General Steelmaking ........................................................................................................ 6
2.1.1 Electric Arc Furnace.................................................................................................. 6
2.1.2 Ladle Furnace Refining ............................................................................................. 7
2.2 Refining Processes ........................................................................................................... 8
2.2.1 Deoxidation ............................................................................................................... 8
2.2.2 Alloying..................................................................................................................... 8
2.2.3 Stirring....................................................................................................................... 9
2.3 Desulphurisation............................................................................................................... 9
2.3.1 Thermodynamic Theory ............................................................................................ 9
2.3.2 Slag Properties......................................................................................................... 12
2.3.2.1 Composition ......................................................................................................... 12
2.3.2.2 Sulphide capacity ................................................................................................. 15
2.3.2.3 Oxides Activities .................................................................................................. 16
2.3.2.4 Sulphur Distribution Ratio ................................................................................... 17
2.3.2.5 Temperature ......................................................................................................... 18
2.3.3 Kinetic Theory......................................................................................................... 18
2.3.3.1 Argon Gas flow rate ............................................................................................. 19
iv
1.0 INTRODUCTION
1.1 Background
Steel and its products are undoubtedly the pillar and anchor of material developments through
the ages. It is a substantial part of material science and a key material in product development
in modern technological advancement. It is the base material for over 2500 different grades of
products
(1)
compositions and several other material properties leads to its wide areas of present use and
continuous possibility of future developments(1).
The world production of crude steel as reported by world steel association is to a great extent
more than any other metal product, this also proves its wide versatility in material
consumption. Its world productions in million metric tons are 1251, 1251 and 1329 in the year
2006, 2007 and 2008 respectively (2).
Figure 1 shows the production of steel in the world in 2008. There was a decrease in the crude
steel produced in the world as well as in Europe and Sweden in 2008 compared to 2007. The
production of steel in Sweden has been between 5.2 and 6 million metric tons in the past 6
years with minimum of 5.2 in 2008 (2).
The production of steel could be classified into two, based on the raw materials; ore based and
scrap based raw materials. Steel from iron ore (hematite or magnetite) are mainly produced in
integrated steel mills while steel from scrap based materials are produced in EAF operated
mills. Steel products could also be classified into three based on the composition of alloy
additives; low alloy steel, medium alloy and high alloy steel (1).
The origin of Ovako could be traced to strong Nordic steel production technology and the
forerunners to the company were founded for over 300 years ago. Present day Ovako was
established in 2005 by a merger of 3 re-known steel companies, Ovako Steel, Fundia Steel
and Imatra Steel. Due to strategic and technical reasons, the new company decided to
continue its operation in a specific steel product (3).
Ovako consists of four product divisions namely; Bar, Wire, Bright Bar and Tube&Ring.
Figure 2 below shows the four product divisions with their respective production sites.
Slag Removal
Melting
Scrap Charging
Ladle Furnace
Vacuum
Ingot
To Rolling Mill
Stripping
Ingot Teeming
The steel temperature is finally adjusted to casting temperature and the composition is
checked to be in agreement with the aimed composition. The 100ton refined molten steel is
finally teemed into 24 ingots each of 4.2ton weight using up-hill teeming. The ingots are
stripped and then transported to the pit furnaces for heat treatment prior to rolling or forging.
The final products after processing in the rolling mill and tube& ring mill are in the form of
bar, tube and ring.
The production of steel grades used for the manufacturing of ball bearing requires very low
oxygen content in other to reduce the possibility of formation of non metallic oxide inclusions
such as Al2O3, and etc, which have deleterious effect on the final products (fatigue life, crack
initiation point)
(4)
. A lot of research work has been done on the reduction of total oxygen
content of steel; a successful result achieved was a further reduction from about 20ppm to
5ppm. This success led to the increase in the effect of sulphur in the steel, these effects
become somewhat more intense than earlier noticed (4).
ii.
It lowers the melting point and intergranular strength and cohesion of steel
iii.
Sulphur contributes to the brittleness of steel and when it exists in sulphide phase it
acts as stress raiser in steel products. (4,5)
the low sulphur requirement ranges of the different steel grades but with a low level of
accuracy. These involve extra sulphur addition when the sulphur removal is too high or
further refining when the removal is too low.
However the focus of this project work is to improve the desulphurisation process during
vacuum degassing at the ladle furnace, by slag composition control. It is focussed on
increasing the level of accuracy of the process to meet the desired sulphur content of the steel
product and also to shorten the degassing period. This involves an extensive study of the
thermodynamics of the process and kinetics. The ladle refining of different steel grades and
different slag practice were followed daily. Slag properties (especially composition), steel
compositions, temperature and some other factors were analysed for their sulphur removal
potential using some empirical models and later compared with actual measurements in the
plants. The compositional variation of the slag formed after deoxidation was studied with
respect to the dissolved oxygen content of the steel at tapping. The mass of slag remaining
after deslagging and its influence on the final slag composition were also investigated.
Optimum synthetic top slag practice with improved sulphide capacity, for accurate
desulphurization for different steel grades was to be estimated and the effects of the different
kinetic parameters were to be investigated.
Slag Foaming
This is a common praxis in the EAF. Carbon or coke is injected into the furnace to increase
the melt down efficiency by supplying additional energy from combustion with injected
oxygen and also to cause carbon boil which promotes stirring to achieve a good slag/metal
mixing. Another important function of this praxis is to cause a foaming of the slag provided
the viscosity of the slag is not too low. The slag foam decreases the energy loss, decreases
refractory wear and protect the water cold panel at the top of the vessel (1, 7).
The injection of oxygen performs some refining operation in the EAF, especially phosphorous
removal although manganese, silicon, chromium and iron are also oxidized. The oxygen
content of molten steel is often extrapolated using the carbon content in an online production
process. In theory dissolved oxygen and carbon content of steel will react to form carbon
monoxide until equilibrium is reached
C + O = CO(g)
(7)
heating, deslagging, wire feeding, stirring with gas or electromagnetic fields and vacuum
treatment (5, 7).
The units of operation mentioned above enables the following refining and adjustment
operations;
i.
Deoxidation
ii.
Alloying
iii.
iv.
Desulphurisation
v.
vi.
vii.
2.2.1 Deoxidation
The oxygen content of the steel tapped into the ladle after melting in the EAF is often high, as
oxygen is injected into the EAF for refining, slag foaming, and other process control
measures. Final steel products require a very low content of oxygen and also further refining
and alloying are most desirable at the minimum oxygen content, for this reasons there is a
need to kill or deoxidize the crude molten steel. The addition of strong deoxidizers such as
aluminum and ferrosilicon is done during tapping, they could either be placed in the preheated
ladle before tapping or run into the tapping stream so as to utilize the mixing effect of the
tapping stream to achieve thorough deoxidation
(5,8)
and (4), and the oxides nucleate to diffuse to the ladle wall or absorbed into EAF slag.
2Al + 3O = Al2O3(slag)
G = -1205115+386.714T ------------------------------------(3)
Si + 2O = SiO2 (slag)
The deoxidation reactions shown in equations (3) and (4) are exothermic and thus the
temperature of the liquid steel is increased, however the steel also loses heat by radiation from
the top surface, heating of ladle lining and by flux through the lining and shell (5). The rate of
heat loss is reduced in most ladle operation by preheating the ladle before tapping.
2.2.2 Alloying
The adjustment of the final composition of the molten metal is done at the heating and wire
feeding position of ladle station. A wire feeder runs wire of alloying elements at controlled
speed into the steel
(5,7)
. Most of the alloying elements are lumpy ferroalloy since they are
cheaper to produce and available in different grades to suit the final steel compositional
requirements. The addition of alloying elements results into temperature drop of the molten
steel and the calculation to meet the final composition is often done by computer
programmes.
2.2.3 Stirring
Generally, ladle furnace technology is equipped with either one or both of the two stirring
facilities; electromagnetic accessory for inductive stirring and permeable refractory block at
the bottom of the ladle called porous plugs for gas stirring. These two stirring means are
important for good metal/slag interaction to achieve an effective ladle refining. It enhances
homogenous temperature and composition of the steel. It also aids continuous slag metal
reaction with the aim of sulphur, hydrogen, nitrogen and inclusion removal (6).
2.3 Desulphurisation
Desulphurisation is an essential practice in the production of clean steel products such as
bearing steels with high fatigue strength which function under high impact operational
requirement. Ovako Steel AB specializes in the production of bearing steel products,
desulphurisation becomes an important subject to be continuously investigated for highly
clean products which can withstand market competition and satisfy customer's demand.
Based on the production route and the type of steel product, desulphurisation could be done at
different points in the steelmaking process and with different reagents; however it is mainly
carried out in a reducing conditions when the oxygen activity is low(8). At Ovako Steel AB,
desulphurisation is done during the vacuum degassing in the ladle furnace using lime
saturated multicomponent slag.
The parameters which influence the desulphurisation process are either thermodynamic or
kinetic parameters; the main parameters are discussed later in the report while the theories
related to this project work are explained below.
[S ] + (O 2 ) = [O] + (S 2 )
( )
(5)
( )
1 2 S ( g ) + O 2 = 1 2 O( g ) + S 2 (6)
[S ] + 1 2 O( g ) + = [O] + 1 2 S( g ) (7)
The equilibrium constant for the reaction in equation (6) is expressed as;
K6 =
K6 =
aS 2
aO 2
PO 2
PS 2
f S 2 (% S )slag
aO 2
PO 2
PS 2
(8)
Cs =
K 6 aO 2
f S 2
C S = (% S )slag
(9)
PO 2
PS 2
Where [S] and [O] are dissolved sulphur and oxygen in the steel respectively while (S2-) and
(O2-) are sulphide and oxide (with free oxygen ion) in the slag respectively. aS2- and aO2- are the
activities of sulphide and oxide in the slag. K6 is the equilibrium constant for gas-slag reaction
in equation (6) (4, 8, 9).
Since oxides activities and the partial pressure of gaseous phases are not readily available as
process parameters, sulphide capacity is often expressed in terms of temperature and
composition as process control tool (5, 13').
Sosinky and Sommerville derived an expression to correlate optical basicity with sulphide
capacity at temperature range between 1400 andd 1700C (4, 14).
22690 54640
Log C S =
+ 43.6 + 25.2 (10)
T
X is the mole fraction of the oxides in the slag system, n is the number of oxygen atom in a
molecule of each oxide and th represents the optical basicity of each oxide (14).
Young et al showed that equation (11) only applied to range where = 0.8, and therefore
reported correlations for ranges with < 0.8,
10
Andersson et al (4) studied the distribution of sulphur and the extent of sulphur removal using
equation (7)
K7 =
aO
aS
PS2
PO2
Also, Log K 7 =
LS =
aO
(% S )
[% S ] f S C S
935
+ 1.375
T
(%S )
[% S ]
Log LS =
935
+ 1.375 + Log C S + Log f
T
Log aO (13)
To calculate the activity coefficient of sulphur in the metal, Wagner's expression can be used
Log f S = eij [% i ] .
(14)
aO and aS are the activities of oxygen and sulphur in the molten steel respectively. eSj , is the
interaction parameter between sulphur and other elements j in the steel. K7 is the equilibrium
constant for the gas-metal reaction in equation (7).
The activity of oxygen in the steel could be calculated assuming equilibrium between the
dissolved oxygen and aluminum in the steel and alumina in the slag or alumina inclusion in
the steel bulk.
Al + 3O = Al2O3
a Al2O3
G
K15 = exp
=
2
RT a Al aO
[ ][ ]
Where aAl2O3 is the activity of alumina in the slag or as inclusion, and aO and aAl are the
activities of oxygen and aluminum respectively. The activity of Al can be calculated using
equations (14) and (16) while the alumina activity can be calculated using Ohto and and Suito
empirical expression in equation (17). aAl2O3 is taken to be 1, if alumina inclusion is
considered in the equilibrium. K17 is the equilibrium constant for the deoxidation reaction
shown in equation (15) (4, 15).
a Al = f Al [% Al ]
Log a Al2O3 =
(16)
% SiO2
The oxide composition is in weight percent and the expression has been proven to be valid for
temperature ranges close to 1600C
(4)
11
60wt%,SiO2; 10-50wt%, Al2O3;0-50wt% and MgO: 0-30wt% which is a fairly good range for
the slag studied in this project work
(16)
2.3.2.1 Composition
The different phases in a multi-component slag system play significant roles in ladle refining
with focus on desulphurisation.
Any composition within the homogeneous liquid region with an activity of CaO close to unity
is good for desulphurisation process. For the system considered in Figure 4, liquidus line 'ab'
represents a perfect unity of CaO activity.
12
1600C
Figure 5, 6 and 7 show the activities of CaO, SiO2 and Al2O3 respectively at different points in
the homogeneous liquid region of the slag system at the 1600C. An optimum slag
composition for good desulphurisation can be carefully chosen by exploring these diagrams to
have the highest possibilities of CaO activity, basicity and efficient fluidity. It should be noted
that composition affects viscosity of the slag, if the CaO of the multicomponent slag system is
higher than 60% it has a negative effect on the sulphide capacity of the slag as it becomes
heterogeneous and more viscous, thus the kinetic will be negatively influenced (6).
13
14
(19)
the sulphur distribution ratio between slag and metal at equilibrium. Its ability to compare the
desulphurization characteristics of different slags has led to the creation of several models for
its measurement
a
b
Figure 8: Isothermal section of the system, CaO-SiO2-Al2O3 at 1650C
showing the Log of Sulphide capacity with composition in mass % (14)
15
Basicity is defined in its simplest form as the ratio of %CaO / %SiO2, it is known that
desulphurization is improved with slags of higher basicity. Basic slags have high content of
basic oxides which are network breakers with ability to release its oxygen ion (O2-) in
exchange for the dissolved sulphur in steel. Significant correlations have been made between
sulphide capacity and basicity. Figure 9 shows three different sulphide capacity models;
Sosinky & Sommerville, Young et al and KTH models. The first two models were calculated
from optical basicity while the third is a model developed in the division of process
Metallurgy in KTH (4). The three models in figure 9 show that sulphide capacity is improved
with increased basicity.
In this project work optical basicity, a measure of the electron donor power of slag will be
used in the estimation of the sulphide capacity, because its model have been proven to have a
fair agreement with empirical data and the parameters can be accessed.
(10)
equilibrium activity of oxygen in the steel and also the basicity of the slag. Figure 10 shows
that at high basicity, the activity of alumina is low and the oxygen activity will also be low
provided the Al content of the steel is high at this condition. This is a necessary requirement
16
for desulphurization. Also Turkdogan E. established that low SiO2 content of the slag is
favorable for improved sulphur removal, due to its equilibrium with Al and Si content of the
steel. (20).
Figure 10: Alumina activities for typical ladle furnace slag using the
KTH model and Ohta and Suito Equation (16).
2.3.2.4 Sulphur Distribution Ratio
It is an estimation of the sulphur reduction in a desulphurization process. It is the ratio of the
sulphur content in the slag and metal phase at the end of vacuum treatment. A good
estimation of this parameter indicates a good control of the process. It is a function of
temperature, sulphide capacity of the slag, oxygen activity and sulphur content of the molten
steel (16). An optimized slag which can be used to control desulphurisation can be obtained by
exploring the ternary diagram shown in figure 11
17
2.3.2.5 Temperature
An essential parameter in desulphurization is the temperature at which the process is carried
out. It influences the viscosity (favourable kinetic condition) and sulphide capacity of the slag
and also sulphur distribution in the metal and slag. Most models that have been developed to
evaluate the sulphide capacity of slag were mainly functions of temperature and composition
(10,11,12,17)
calculation was done at constant MgO and SiO2 contents of the slag and also at constant %Al
and %C content of the steel(11). It is also reported that desulphurisation is slower at the later
period of vacuum degassing due to reduced sulphur content of the steel and temperature drop
during the process which is unfavorable for the sulphide capacity (4).
(12, 19)
18
J = D
[% S m ] [%Si ]
V[% S ]
= D
A t
[% S ] K t m A
=
[% S m ] [% Se ] (19)
t
M
Where
J- Diffusion flux
D- Diffusion constant
- Concentration gradient
x
[% S m ] Initial Concentration of Sulphur in the melt %wt
(12)
. The
conventional assumption of a flat and horizontal slag metal interface area 'A' has been proven
to be an under estimation as the slag is dispersed in the steel and the interaction area is more
than supposed (12).
19
Figure 13: Steel Desulphurisation during Vacuum treatment at various Ar stirring rates (13)
The position of the inductive stirrer and the rate of flow of argon gas through the porous plugs
were studied by Hallberg et al
(17)
Ovako Steel AB. It could be deduced from figure 14 that argon gas flow rate through the
porous plug has an influence on the fluid flow in the ladle, a low flow rate at the first porous
plug which is closer to the inductive stirrer and high flow rate at the second porous plug
which is at the opposite side is necessary for a good desulphurisation (17).
Figure 14: Influence of different argon gas flow rates on sulphur removal for
combined gas and inductive stirring (17)
20
Most of the top slag is concentrated above the second porous slag where they are hit by the
gas plumes from the plug and thus a greater contact area between slag and steel is created.
This is substantiated by the authors, using computational fluid flow dynamic predictions. It
should be noted that the flow rates through the porous plugs are not fixed throughout a heat at
Ovako Steel AB, they are changed by the operators based on reactions observed in the camera
view.
Some previous projects done at Ovako Steel AB have also investigated the effects of argon
gas stirring before and after vacuum treatment on desulphurisation (6). The control of argon
gas flow rate was difficult at the heating station of ladle due to poor flow of gas through the
porous plug. The only trial that was done was unsuccessful with a poor sulphur removal and
poor vacuum treatment.
Another trial with inductive stirring and calm argon gas stirring at the final heating unit
process after the vacuum treatment shows no influence on the final sulphur content of the
steel though it had a positive impact on inclusion removal (6).
2.3.3.2 Viscosity
It is a thermo-physical property that influences the kinetics of the ladle metallurgy
(16)
. The
viscosity of both the steel and slag affects the mass transfer during the ladle refining. At low
viscosity of the slag, mass transfer rate of sulphur is improved due to easy dispersion in the
steel and the slag/metal interfacial area is increased
(13)
can be synthesized by adding a correct proportion of Al2O3, and the viscosity is adjusted in
some steel plants by the addition of CaF2. (6,13). Viscosity values for steels are reasonably well
established at steel making conditions but the viscosity of slags are not, they are rather
extrapolation of temperature and composition in a multicomponent slag system (16).
21
removal. A preliminary study of the process shows the following possible sources of the
dilution slag;
1. EAF Slag: Hot heel is a common praxis at Ovako steel, about 110tons of steel scrap is
charged into the EAF and less than 105tons is tapped into the Ladle leaving some steel behind
in the furnace. Despite the hot heel practice, it is unavoidable to have a small mass of slag
entrained in the tapped steel.
2. Tap hole sand: After each tapping, the tap hole is blinded with Olivine sand. It is of course
certain that this sand will be lost into the steel during tapping, as the hole is opened before
steel falls into the ladle. The tap hole sand is rich in MgO and SiO2 and its quantity in the
tapped stream depends on the age of the tap hole, this also considered as a probable source of
dilution slag during ladle refining.
3. Ladle glaze: Ladle glaze is formed when draining the Ladle into the mould, as top slag
comes in contact with refractory (21). As teeming proceeds the temperature of the system drops
and fluidity of the slag reduces, thereby forming non metallic particles after reacting with
refractory, this particles hang on the wall of the ladle as glaze and are flushed off when liquid
steel is poured into the Ladle during subsequent heat. The condition, composition and the
amount of the glaze depends on the steel type produced at a particular heat.
4. Deoxidation Products: To enhance further refining after melting of scrap in the EAF,
reduction of oxygen contents of the steel is important. The oxygen contents which is often
between 100 and 1000ppm before tapping depending on the extent of refining and the heat
condition in the EAF, is reduced by the addition of aluminium metal and Ferrosilicon alloy.
The reaction products, Al2O3 and SiO2 indigenous inclusions are major sources of inclusion in
steel making and as well increase the amount of the EAF slag as they are absorbed after
nucleation and separation from the steel bulk.
With consideration to all the theories of sulphur removal as well as thermodynamic and
kinetic properties discussed earlier, this project work will advance sulphur removal process at
Ovako steel AB Hofors using slag composition control. It will investigate the slag mass and
composition during different process stages and attempt to optimize the slag with the aim of
controlling sulphur refining process.
22
The additives used in the process includes anthracite, coal, oxygen, slag formers (Lime,
dolomite Alumina and pure Alumina), deoxidants (Aluminium metal and Ferrosilicon) and
other alloys. The chemical composition of the slag formers used at the ladle furnace refining
is given in table 1.
Table 1: Chemical Composition of slag formers
Lime
Alumina
SiO2
2,91
2,78
2,22
Pure Alumina
Measurement is in wt-%
MnO
0,17
0,08
0,02
S
0,065
0,017
0,006
TiO2
0,050
0,198
0,020
CaO
92,30
17,58
4,22
Al2O3
0,93
63,78
91,90
MgO
0,80
12,13
0,45
FeO
0,430
0,679
3.2 Method
23
Eight sampling points were observed at different subunits in the integrated process line for
thorough follow up of the equilibrium conditions and changes in the system. The schematic
diagram of the sampling points is shown in Figure 15.
1. B1, S1, O1, T1: Steel sample, Slag sample, Oxygen activity and Temperature in the
EAF just before tapping respectively
2. B2, S2 : Steel sample and Slag sample at the end of tapping;
3. S3: Slag sample before slag removal
4. B4, O4, T4 : Steel sample, Oxygen activity and Temperature at arrival at the ASEASKF Ladle furnace station before alloying
5. B5, S5, O5, T5 : Steel sample, Slag sample, Oxygen activity and Temperature before
degassing
6. B6, S6, O6, T6: Steel sample, Slag sample, Oxygen activity and Temperature after
degassing.
7. B7, S7, O7, T7: Steel sample, Slag sample, Oxygen activity and Temperature after
extra alloying (if there is any).
8. B8 : Steel sample during casting.
24
Chemical Composition Steel Samples: Automatic lances, similar to the temperature lances
said earlier were used to take steel samples at each point mentioned above, the samples were
sent to the operation laboratory were immediate analysis was made. The samples were
analysed by optical emission spectroscopy (Bausch & Lomb, ARL OES 4460) for the
concentrations of Al, Cr, Mn, Si, P, Mo, V, Ca, Ti, Mg and other minor elements. The relative
analysis accuracy of these elements depends on their concentrations. Sulphur and carbon in
the samples were analysed with LECO CS-444 using the melting and combustion method.
Chemical Composition of Slag Samples: The slag samples were taken at each designated
process stage using the slag spoon, the samples were saved for further analysis. The samples
were prepared before analysis; they were ground into powder in a ring mill, sieved to collect
fine particles less than 10m which are void of metallic iron. Chemical reagents were added
according to standard and then thoroughly mixed together. The prepared samples were then
heated in a laboratory furnace for about 8 minutes before they were arranged in the PAN
analytical Axios equipment to analyse the oxide composition using the wavelength dispersive
X-ray fluorescence technique. The concentration in weight percent of CaO, Al2O3, SiO2,
MgO, MnO, TiO2, Cr2O3 and other oxides in minor concentration were measured. A portion
of the samples taken after grinding to fine size was also analysed for sulphur and carbon
content. This analysis was done in LECO-CS 200 equipment using the melting and
combustion method.
25
Oxygen content
The dissolved oxygen content in the steel bulk is a key parameter in refining during steel
making process. In the project work the activity of oxygen in the steel melt was measured
using the Celox sensor designed by Heraeus Electro-Nite. The sensor contains ZrO2 elctrolyte
with a molybdenum wire in Cr/Cr2O3 as a reference electrode while the bulk steel is the
second electrode. An electromotive force (e.m.f) is built up when different oxygen activities
are sensed by the two electrodes, the value of which is displayed on the screen of the
equipment. The thermocouple attached to the sensor measures the temperature of the system.
A calculation is generated automatically using the measured temperature and e.m.f to obtain
the oxygen activity which is then displayed on the screen of the equipment.
26
CaO
Al2O3
SiO2
MgO
TiO2
FeO
MnO
Synthetic slag 1
66,23
22,79
2,77
4,48
0,05
0,110
0,59
0,14
Synthetic slag 2
62,50
25,92
2,75
5,00
0,04
0,12
0,62
0,13
68,52
25,49
2,18
0,71
0,05
0,04
0,31
Synthetic slag 1: 65%Lime&35% Alumina, Synthetic slag 2: 60%Lime&40%Alumina,
Synthetic slag 3: 73%Lime&27% Pure Alumina (Measurement is in wt-%)
0,13
Synthetic slag 3
27
C aO %
A l2O3 %
33
65
SiO2 %
10,0
30
60
27
7,5
55
24
50
5,0
21
MnO %
FeO %
4
MgO %
8
3
6
Figure 16: Box Plot-Investigating the variation in the top slag composition before Degassing
where
and
represent
%SiO2
1
2
3
6,80
10,00
5,60
%MnO
%CaO
0,24
3,14
0,18
57,30
49,80
64,50
26,00
27,40
28,40
8,20
7,50
2,50
62,00
59,01
55,10
60,40
56,70
63,50
56,60
59,00
56,50
58,37
4,01
6,87
26,60
25,40
26,70
24,10
31,90
28,00
21,90
25,50
27,90
26,65
2,47
9,26
3,20
6,02
8,00
6,80
4,90
3,30
6,70
5,70
8,10
5,91
2,03
34,30
4
6,90
0,84
5
6,28
3,49
6
7,50
0,77
7
5,10
0,23
8
6,20
0,40
9
5,90
0,31
10
9,20
1,20
11
7,20
0,13
12
6,40
0,09
Mean
6,92
0,92
Std dev
1,43
1,17
Rel dev.
20,62
127,51
The composition is measured in wt-%
%Al2O3
%MgO
%FeO
ao(ppm)
Temp C
1,66
2,21
0,61
2,8150
4,1400
2,4140
1610
1596
1624,7
1,24
3,46
0,81
2,60
1,00
0,73
3,90
0,70
0,33
1,60
1,18
73,76
5,1205
3,6064
2,5326
3,0263
3,4036
2,0369
3,1259
1639
1610
1606
1597
1625,9
1618,7
1577,9
1608,6
The higher extreme values for the CaO in the box plots (though not considered as outliers for
the distribution), are connected to high proportion of lime in the synthetic slag blend and also
high mass of the synthetic slag (this is a common practice for high clean steel which requires
extreme sulphur removal). The lower extreme values are peculiar for heats with high oxygen
activities ao at tapping; which implies a low yield of Al and Si at tapping and also higher
potential to retain some deoxidation products as inclusion in the steel bulk or on the ladle wall
28
until ladle refining stage when they are removed to the top slag. For %Al2O3, the outlier is an
uncommon blend of slag former (68% Lime and 32% pure Alumina) which contains very
high %Al2O3 . On the contrary MnO, FeO and SiO2 have high relative deviation with wide
spread of the values and most of the values close to one extreme end. This is an indication that
their compositions in the topslag are not controlled by the variation in the slag former blend.
The upper extreme values for these oxides contents are results of high ao at tapping, Al/O/
Al2O3 equilibrium before vacuum degassing and also the quantity of carry over slag remaining
after the mechanical slag removal. The lower extreme values, especially for SiO2, depict special
heats with high purity requirements; they are refined with synthetic slag former of high mass
and low initial SiO2. The SiO2 content of the slag of such heats is reduced further during
vacuum treatment as the interaction between slag and steel degassing became improved. This
reduction (equation 21) is aided by high %Al and low ao of such heats, and it in turn favours
good desulphurisation.
The trend for the variation of MgO from 2.5 to 8.2% is a little bit compounding, as it depends
on the amount of EAF slag remaining after slag removal, age of the ladle in use, lime saturation
of the top slag and it also depends on the slag former blend. If pure Alumina is used, then the
MgO content of the top slag before vacuum treatment will be very low due to the low content of
MgO in it. It can be clearly seen from figure 17 that the solubility of MgO refractory into the
topslag varies with CaO content of the top slag; lime saturated topslag has a low solubility
potential of the refractory and vice versa. It was observed that the ladle age is also an
influencing factor for the MgO content of the topslag before vacuum treatment. Newly lined
ladles have greater potential to wear than old ladles though they give better thermal resistance
and heat conservation than the old ladles.
%MgO
7
Before Degassing
After Degassing
1
45
50
55
60
65
% CaO
Figure 17: MgO pick up from the refractory into the top slag
29
Furthermore, an attempt was made to calculate the elemental mass balance between the steel
and slag for each of the heats just before vacuum treatment during the ladle refining. The
results shows that extra slag was often added to the steel during heating and inductive stirring.
The optimum inductive stirring power of about 1000W together with the new top slag
composition often enhanced the lifting up and absorption of the inclusions (from deoxidation
products attached to the ladle wall), ladle glaze and also EAF slag that clustered on the ladle
walls, into the top slag.
In the mass balance, mass input was not equal to mass output due to the influence of the carry
over slag. The elemental mass difference in the steel and top slag could be said to be a result
of the carry over slag whose composition is unknown. Table 4 shows the mass difference of
some selected elements, before vacuum treatment. It could be seen that excess Al, Si as well
as Mg appear into the system in all the heats in the mass balance made just before the vacuum
treatment. (With the exception of heat 3 which could be due to measurement error). This
support earlier observation on the large deviations of SiO2 and MgO contents of the topslag
before degassing, since their initial mass in the slag formers used during refining are small.
For Mn, the additional mass though very small has a meaningful influence on the top slag
composition before degassing. The higher values of Mn in Table 4 are peculiar to heats with
high manganese contents, this could be taken as an error in measurement of Mn alloy, and
these values are less than 5% of the total mass of the alloy added at such heat.
30
Table 4: The mass balance between slag& steel of selected elements before vacuum treatment
Heats
1
2
3
4
6
7
8
9
10
11
12
Si
15,12
30,13
23,68
32,52
15,90
6,32
11,79
22,10
16,29
14,71
Mn
6,39
39,56
6,72
-38,94
-50,47
4,63
5,09
-3,15
-16,09
3,98
4,92
S
-0,08
2,22
-1,40
1,65
-2,89
1,78
-1,66
-0,32
-0,40
2,77
Ti
0,51
0,69
-0,05
-0,17
0,46
0,71
0,71
0,17
0,81
0,46
0,67
Ca
0,02
-0,01
0,02
0,01
0,01
0,13
0,06
0,00
0,02
0,06
0,04
Al
26,32
4,90
8,27
7,04
11,53
61,31
8,63
-3,02
18,35
26,83
Mg
27,81
25,88
14,21
20,90
25,24
14,91
8,58
20,75
16,37
9,26
26,56
Extra
Slag
146
256
74
130
165
82
164
93
137
97
149
*Heat 5 was not recorded because no sample was taken at sample point 4, and thus mass balance was incomplete
*All calculations are in Kg
The mass balance done in this work, only gives an idea of an upward flow of oxides from the
steel to the topslag as well as the reduction of oxides into the steel. It is difficult to calculate a
perfect mass balance at some points because the reactions proceed rapidly until equilibrium is
achieved. The assumption of fixed mass of CaO in the slag before degassing also influences
the result of the mass balance, the values are not extremely precise but the trend is good for
analysis.
A plot of the influence of the independent variables on the heats is shown in figure 19 (score
plot), the heats with high slag former are grouped together in a direction of low SiO2 contents
(high CaO content) while the heats with low %C at tapping (high ao) tends in the opposite
direction favouring high SiO2 content (low CaO content) of the top slag.
X
Y
M1 (PLS)
w*c[Comp. 1]/w*c[Comp. 2]
0,80
Slag forme
0,70
0,60
0,50
0,40
CaO_degas
Al(kg)
w*c[2]
0,30
0,20
0,10
Temp
0,00
Si Yield
Al Yield
-0,10
SiO2_degas
-0,20
Si(Kg)
C
-0,30
SiO2
CaO
-0,40
Extra slag
-0,50
-0,50
-0,40
-0,30
-0,20
-0,10
0,00
0,10
0,20
0,30
0,40
0,50
0,60
w*c[1]
M1 (PLS)
t[Comp. 1]/t[Comp. 2]
N3589-803Q
3
N5944-277Q
t[2]
N3614-803F
N5902-804Q
N6192-803F
N3620-803Q
N3677-803Q
N3634-803Q
N3601-803Q
N3602-255G
N6067-803Q
N6206-803F
-1
-2
N3622-803F
N6145-143A N6040-123A
N5857-824B
N6174-803F N6236-824B
N6052-280T
N6066-803F
N6204-825B
N6208-803J
N5858-256G
N6175-826B
-3
-4
-4
-3
-2
-1
t[1]
32
The contribution of each of the independent variables to the model for the prediction of the
SiO2 and CaO content of the top slag is shown in figure 20. The most important parameters
influencing the top slag composition before degassing as shown by the VIP plot below are;
amount of the synthetic slag former added, amount of carry over slag, yield of the deoxidants
into the steel and the carbon content at tapping (oxygen potential).
M1(PLS),
VIP[Comp. 2]
VIP[2]
Temp
Si(Kg)
CaO
SiO2
Al(kg)
Al Yield
Si Yield
Slag forme
Extra slag
Var ID (Primary)
In summary the model created shows a fairly good explanation of 0.64 for the variation of the
dependent variable (CaO and SiO2) in all the observed heats, but it has a poor predictability of
0.34. This implies that the model is unreliable to predict the composition of the top slag
before degassing for any arbitrary heat besides the heats observed. The reason for this is that,
some other important variable parameters were not involved in the PLS regression, this
parameters include the description of the ladle glaze, amount of EAF slag tapped, mass of the
EAF slag removed and mass of refractory wear. Similar regression was done for the
prediction of Al2O3; the model was also mostly described by the same important parameters
as observed for CaO and SiO2.
33
(4)
calculate the Al2O3 activities in the slag while Wagner's expression in equation (16) was used
to calculate the Al activities in the steel. The values of the interaction coefficients used were
taken from T. A Engh (8).
The second model assumed equilibrium between Al and O dissolved in the steel and Al2O3
inclusion in the steel bulk, for this model the activity of Al2O3 inclusion was assumed to be 1
since at this stage of refining ( before degassing) it is valid to consider that the inclusion is
Al2O3 saturated (15).
In the third case a model was created using several existing online process data (measured ao,
temperature and %Al in the steel) to predict the ao at a particular temperature and within an Al
range.
Appendix XI shows graphical relationship between ao and %Al in the melt at different
temperature. The formula obtained in the model fit in appendix XI was used in the third
model calculation. Figure 21 shows a comparism of the three models with the measured ao
values. Model 2 and 3 gave fairly close values compared with measured values while model 1
shows a high discrepancy.
34
5,0E-04
ao(ppm)
4,0E-04
Ohta&suito
3,0E-04
Al2O3 =1
Data
Measured ao
2,0E-04
1,0E-04
0,0E+00
0
10
12
14
Heats
It could be seen from figures 21 and 22 that model 2 which assume equilibrium between
Al/O/Al2O3inclusions has a quite close pattern with the measured ao values and also has a high
degree of explanation for the deviation of its values from measured value. It has a good
Calculated ao
5,0E-04
y = 0,1363x - 1E-05
R2 = 0,4968
4,0E-04
y = 0,7739x + 2E-06
R2 = 0,8197
3,0E-04
y = 0,4968x + 0,0001
R2 = 0,6223
Ohta&suito
2,0E-04
Al2O3 =1
Data
1,0E-04
0,0E+00
1,00E-04
2,00E-04
3,00E-04
4,00E-04
5,00E-04
6,00E-04
Measured ao
35
A refit of these models was done and the modified models gave better ao prediction as seen in
figure 23 below.
6,00E-04
5,00E-04
ao (ppm)
4,00E-04
Ohta&suito
Al2O3=1
Data
3,00E-04
Measured ao
2,00E-04
1,00E-04
0,00E+00
0
10
12
14
Heat
For online utilisation of ao values, it could be inferred from the investigation above that model
2 gives a fairly accurate result with better predictability.
calculated using Young et al expression, written in equation (12) but in few cases when
optical basicity is very close to 0.8, Sosinky & Sommerville expression was used due to better
correlation (14).
Figure 24 shows the values of measured and calculated sulphur distribution ratio after vacuum
treatment. The calculated Ls gives the probable sulphur distribution at equilibrium, while
measured Ls gives the actual distribution at the prevailing kinetic conditions. A perfectly
36
linear correlation could not been observed from figure 24 because equilibrium was not
reached after vacuum treatment for few heats. This could be explained by kinetic reasons of
either short time or poor interaction between the reacting phases. Calculated Ls is the sulphur
partition value at optimum desulphurisation condition, i.e. assuming favourable kinetic
conditions such as low vacuum pressure, optimised argon gas purging and good viscosity.
The optimum vacuum pressure (<5 torr) was always attained during the plant trials but an
investigation of the gas flow for all the heats shows that argon gas flow rate has a major
influence on the success of the desulphurisation.
1200
1000
Measured Ls
800
600
400
200
0
0
200
400
600
800
1000
1200
1400
Calculated Ls
Figure 24:
The heats in figure 24 with lower values of measured Ls compared to calculated Ls have poor
gas stirring. For most of these heats the average flow rate of argon gas in either/both porous
plugs was lower than 45ltr/min as opposed to about 80ltr/min for others and 100ltr/min
suggested by Hallberg et al
(17)
slag after desulphurisation is inhomogeneous, this influences the measured Ls; this is
supported by previous investigation done by Andersson M. et al (4).
37
[%Si ] [%S f ]
X 100
[%Si ]
(20)
Where [%S]i is the Initial sulphur content of steel before degassing while [%S]f is the final
sulphur content of steel after degassing.
An overview of the model is shown in figure 25 and figure 26. From the loading plots of the
predictor in figure 25, it could be seen that the tendency of having a very high DD is favoured
by high mass of slag former, longer time of degassing good argon gas flow through the
porous plug, %Al in the steel and the cross interaction between CaO&Al2O3. An increasing
basicity is also very important to obtain good desulphurisation but it requires high slag mass
to achieve an extreme desulphurisation. The SiO2 content of the top slag has a negative
influence on DD. The score plot of the observed heats in figure 26 shows an outlier heat, the
DD predicted by the model from the x-variable parameters of this heat does not correlate with
measured DD, and this is as a result of unusually low Al2O3 and very high CaO content in the
top slag and also very poor argon gas flow rate. The figure also shows the grouping of all
heats into extreme sulphur removal and low sulphur removal, this is explained by the
x- variable contributions in each heat.
38
X
Y
Cross
M1 (PLS)
w*c[Comp. 1]/w*c[Comp. 2]
Ar 2
0,40
SiO2
ao
Ar 1
0,30
DD Temp
0,20
Time
w*c[2]
0,10
Slag forme
CaO*Al2O3
CaO/Al2O3
0,00
-0,10
CaO
Al2O3
%Al
-0,20
-0,30
fs
-0,40
-0,10
B1
0,00
0,10
0,20
0,30
0,40
w*c[1]
3
N5858-256G
N3622-803F
N6204-825B
N6145-143A
N6052-280T
N3602-255G
t[2]
N3614-803F
N5944-277Q
N6040-123A
N3601-803Q
N3620-803Q
N3677-803Q
N6067-803Q
N3634-803Q
N6236-824B
0
N5857-824B
-1
N6192-803F
N3589-803Q
N6066-803F
N6175-826B
N6174-803F
N6208-803J
-2
N6206-803F
N5902-804Q
-3
-6
-5
-4
-3
-2
-1
t[1]
The contribution of each of the independent variables to the model for the prediction of the
DD is shown in figure 27. The most important parameters influencing the DD as shown by
39
the VIP plot of the model are; time, temperature, mass of slag former, %Al, basicity, slag
composition, oxygen activity and argon gas in the second porous plug.
M1 (PLS)
VIP[Comp. 2]
2,00
1,80
1,60
1,40
VIP[2]
1,20
1,00
0,80
0,60
0,40
CaO/Al2O3
fs
CaO
Al2O3
ao
SiO2
B1
CaO*Al2O3
Ar 1
Ar 2
%Al
Slag forme
Temp
0,00
Time
0,20
An observation from this PLS regression analysis worth mentioning is the influence and
importance of the ao in the model. Oxygen activities ao is dependent on temperature, so it is
difficult for PLS model to show the precise influence of ao on DD. It is expected that high ao
should have a negative influence on DD but this could not be clearly seen on the model
overview, since the degassing for all the heats were not carried out at the same temperature.
Heats with longer degassing time usually commenced at higher temperature for the reason of
favourable kinetics during the length of degassing, this however made it difficult to see the
expected influence of ao on DD in this simple model.
40
The reduction reaction is shown in equation (21), the forward reaction is favoured if the Si
content of the steel is low and the Al content is high and with a rigorous argon gas stirring (20).
For the 12 heats investigated, the influence of the above mentioned equilibrium condition on
sulphur removal is shown in figure 28. The smooth curve on the graph is the equilibrium
relationship for Al reduction of SiO2 from lime saturated calcium aluminate slag at
temperature close to 1600C, as explained by E. T. Turkdogan (20).
The points on figure 28 explain the drift of the system towards equilibrium during degassing.
Each heats have two points on the curve, the point with higher Al represent the condition
before degassing when equilibrium has not been achieved while the corresponding point with
lower Al depicts equilibrium condition after degassing (though it was suspected that few heats
did not attain equilibrium with the kinetic conditions that prevailed during the process).
41
80
70
60
SiO2/Si
50
40
30
20
10
0
0,000
0,020
0,040
Equil Lit
5
10
0,060
1
6
11
0,080
[% Al]
2
7
12
0,100
0,120
3
8
0,140
0,160
4
9
Figure 28: Aluminium reduction of SiO2 from Lime saturated molten slag during degassing
From figure 28 it could be noted that all the heats are moving towards the smooth equilibrium
curve as the vacuum treatment proceeds, some final points are yet far away from the curve
either due to lower reaction temperature compared to that of the equilibrium curve or
equilibrium has not yet been achieved before the process was stopped.
Heats with high %Al before degassing have low ao and have higher potential for the reduction
of the slag and consequently giving a favourable condition for desulphurisation to proceed.
Heats with low %Al have the tendency for increasing SiO2 content of the slag and increasing
oxygen potential of the system which is unfavourable for sulphur removal.
The initial ao activity before degassing is also another important parameter which influences
the equilibrium drift in the plot. Heats with high ao before degassing have the tendency of
increasing SiO2 of the slag and thereby limiting the extent of the desulphurisation even if the
slag is lime saturated.
42
A mass balance was made in terms of sulphur content of the system at equilibrium, in order to
project the sulphur content of the steel after vacuum treatment. The mass difference of
sulphur in the steel before and after degassing was equated to the mass difference of sulphur
in the slag.
M s [% S ]i M s [% S ] f = M sl (% S ) f M sl (% S )i
[% S ] f
M s (% S )i + M S [% S ]i
(22)
M Sl Ls + M S
Figure 29 shows that few heats have higher measured [%S]f values after degassing compared
to calculated values, similar reasons hold for the observed variation in the measured and
calculated values of Ls explained earlier.
43
0,025
Measured [%S]
0,020
0,015
0,010
0,005
0,000
0,000
0,005
0,010
0,015
0,020
0,025
Calculated [% S]f
The heats with values far away above the equilibrium line are the same heats with wide
variation in Ls, equilibrium was not achieved after vacuum treatment, perhaps due to poor
argon gas stirring or time factor.
It should be noted that some of these deviations observed in the calculated parameters could
be due to the model used in calculating the sulphide capacity of the slags, other models such
as 'IRSID' and 'Thermoslag' could have been used as well but their parameters were not
accessible.
44
The extra slag practice involves the addition of lime (200-400kg), during tapping to increase
the activity of CaO and thus improve the ability of the EAF slag to absorb the entrapped
oxides in the steel. A short inductive stirring is necessary to remove the ladle glaze and other
oxides, and also enhance the upward transport to the slag at the top of the vessel. This practice
will enhance the accurate estimation of slag former with right mass and sulphide capacity for
a precise sulphur removal since dilution of the new synthetic slag would have been reduced to
an insignificant level.
45
All heats have at least 100% increase in the SiO2 content of the top slag before
degassing, including heats with low oxygen potential at tapping, where the yield of
silicon from FeSi into the steel is high. This is an influence of the unknown mass of
slag and oxides remaining on the ladle wall or entrapped in the bulk steel after EAF
slag removal. It was also noted that heats with high oxygen potential before tapping
and low mass of synthetic slag former, have an tendency for increased SiO2 content in
the top slag before degassing
MnO and FeO in the top slag before vacuum treatment are also traced to slag or oxides
entrapped in the steel or on ladle walls. These two oxides appear to be low when low
oxygen activity is achieved after deoxidation at tapping or when the %Al content of
the steel is very high. They are easily reduced by Al.
MgO obviously comes from two major sources; carry over slag and refractory erosion.
Heats for high clean steel, have very low MgO and high CaO in the synthetic slag
blend, this however result in low MgO content of the topslag before degassing as slag
with high CaO has low tendency for the dissolution of the refractory.
The most important factors influencing top slag composition before degassing are
amount of slag former added, mass of carry-over slag, oxygen potential and the yield
of the deoxidants at tapping.
The PLS model created has a very unreliable predictability for the top slag
composition due to lack of other important parameters. This necessitated an alternative
solution of extra slag practice to improve the absorption of oxides in the steel bulk.
A number of heats has lower sulphur partition ratio after desulphurisation compared to
the calculated values due to poor argon gas flow, this is also substantiated in the
regression analysis made.
46
The second regression analysis made shows that the sulphur removal can be optimised
by controlling the following parameters; mass& composition of the top slag, vacuum
treatment time, % Al, oxygen activity in the steel before degassing and argon gas flow
rate.
To achieve a precise sulphur removal with an optimised top slag composition, the
argon gas flow and inductive stirring effect during the vacuum treatment must be
optimised as well.
5.2 Recommendations
The following praxes highlighted below are recommended based on the investigation made in
the research thesis and the prevailing process practices at the steel plant.
It could be a better practice to add extra sulphur into the system only after vacuum
treatment, for heats with high final sulphur requirement, to reduce loss of sulphur into
the slag during vacuum treatment.
The improvement of the argon gas stirring for optimum utilisation of the sulphide
capacity of the slags should be investigated. This will decrease the degassing time and
also contribute to the expected result for precise sulphur removal using slag
composition control.
Further research should be carried out on the mass of lime to be added during tapping
to improve the ability of the EAF slag to absorb entrapped oxides in the steel bulk.
47
REFERENCES
1. D. Janke, L. Savov, H.J Weddige, E. Schulz ; Scrap based steel production and
recycling of steel, Material Technology 34(6)387(2000)
2. World steel Association; http://www.worldsteel.org Feb. 2009
3. Ovako Intranet; http://www.ovako.com
4. Margareta Andersson, Pr G. Jnsson, Mselly M. Nzotta; Application of Sulphide
Capacity Concept on High basicity Ladle Slags Used in Bearing Steel Production. ISIJ
International, Vol 39 (1999) No 11, pp 1140-1149.
5. Encyclopedia Britanica; http://www.britannica.com/EBchecked/topic/564627/steel#,
1996
6. Fredrich Martinsson, Frbttring av svavelrening och avskiljning innan samt efter
vakumbehandling genom spolning med argon vid tillverkning av rent stl; Master
Thesis KTH.
7. Bo Bjrkman, Iron and Steel making course compendium, section2 ; Process
Metallurgy division, LTU.
8. T. Abel Engh, Principles of Metal Refining, Oxford University Press New York.
9. E.T. Turkdogan, Fundamentals of Steel making; The insititue of Materials 1996.
10. Margareta A. Andersson, Lage T.I. Jonsson, Pr G. Jnsson, A thermodynamic and
Kinetic Modelling of Reoxidation and Desulphurisation in the Ladle Furnace; ISIJ
International Vol. 40 (2000), No. 11, pp. 10801088.
11. Margareta Andersson, Pr Jnsson, Malin Hallberg, Optimisation of Ladle slag
Composition by application of a sulphide capacity Model; Iron and steel making
February 2000.
12. Pr Jnsson, Lage T.I. Jonsson, The Use of Fundamental Process Models in Studying
Ladle Refining Operations; ISIJ International, Vol 41 (2001),No. 11,pp1289-1302.
13. Anna Bostrm, A model for Multicomponent reactions between metal/slag using
Thermo-calc, applied for removal of sulphur during the ladle treatment. Licentiate
thesis 1997, KTH.
14. Slag Atlas second Edition, Edited by Verein Deutscher Eisenhuttenleute (VDEh)
15. J. Bjrklund, P Jnsson, Equilibrium conditions between Slag and Steel and Inclusions
during Lalde treatment, Iron and Steelmaking, Vol. 34, No 4, pp312-324, 2007.
48
49
APPENDICES
SiO2 %
MnO %
S %
TiO2 %
CaO %
Al2O3 %
MgO %
FeO %
0,11
0,34
34,70
4,48
9,38
22,27
0,10
0,10
0,11
0,08
0,54
0,68
0,51
0,46
44,1
49,0
45,9
36,7
5,6
5,7
6,4
6,3
10,3
4,8
10,8
15,8
17,6
13,6
8,7
12,6
0,076
0,053
0,12
0,06
0,51
0,51
0,20
0,18
0,18
0,11
35,90
19,20
29,36
23,2
27,3
12,20
27,60
16,71
23,7
25,4
13,40
20,60
14,37
23,9
25,7
15,80
7,56
18,09
5,5
3,5
0,09
0,10
0,11
0,16
0,33
0,60
0,49
0,27
30,9
48,2
41,7
26,1
20
6,0
7,2
14,3
22,1
4,9
12,2
27,0
10,1
12,6
11,1
5,8
0,18
0,08
0,09
0,07
0,07
0,21
0,54
0,84
0,04
0,16
0,25
0,48
0,11
0,19
0,52
0,17
0,14
0,22
0,10
0,14
0,19
0,29
0,28
0,12
28,60
28,20
35,80
22,90
29,44
22,60
31,70
30,50
23,60
40,60
38,20
25,40
24,80
23,90
17,70
33,80
30,38
29,50
25,90
21,60
22,00
20,90
20,30
23,70
22,80
15,30
11,80
16,60
13,88
23,70
22,10
28,20
24,30
12,90
15,20
26,90
2,13
9,62
12,23
6,47
11,93
5,20
3,90
2,50
4,30
4,30
5,10
2,30
ao(ppm)
TempC
136
N/A
632
159
928
1694
1730
1713,2
1703,3
1692,6
50
Heat
Sample
1
2
3
4
5
6
7
8
9
10
11
12
Sample
1
2
3
4
5
6
7
8
9
10
11
12
Sample
1
2
3
4
5
6
7
8
9
10
11
12
SiO2 %
MnO %
S
Before Degassing
6,80
0,24
10,00
3,14
5,60
0,18
6,90
0,84
6,28
3,49
7,50
0,77
5,10
0,23
6,20
0,40
5,90
0,31
9,20
1,20
7,20
0,13
6,40
0,09
After Degassing
8,00
0,04
12,00
0,43
2,10
0,03
5,00
0,10
7,72
0,32
8,70
0,27
5,90
0,05
6,40
0,20
5,80
0,13
8,70
0,09
7,60
0,03
7,50
0,05
at completion of Refining
TiO2 %
CaO %
Al2O3 %
MgO %
FeO %
0,28
0,37
0,23
0,21
0,43
0,52
0,35
0,53
0,15
0,19
0,31
0,86
0,15
0,17
0,07
0,07
0,13
0,14
0,14
0,07
0,11
0,13
0,11
0,14
57,30
49,80
64,50
62,00
59,01
55,10
60,40
56,70
63,50
56,60
59,00
56,50
26,00
27,40
28,40
26,60
25,40
26,70
24,10
31,90
28,00
21,90
25,50
27,90
8,20
7,50
2,50
3,20
6,02
8,00
6,80
4,90
3,30
6,70
5,70
8,10
1,66
2,21
0,61
1,24
3,46
0,81
2,60
1,00
0,73
3,90
0,70
0,33
1,30
1,10
0,77
0,77
1,94
2,40
1,30
1,30
0,75
1,20
0,91
2,10
0,17
0,19
0,12
0,10
0,21
0,23
0,19
0,15
0,16
0,17
0,19
0,21
56,10
49,90
58,70
55,80
52,16
52,50
59,50
52,10
60,60
56,40
59,00
58,30
28,60
29,30
35,30
34,00
29,78
28,60
27,30
32,20
30,20
28,30
27,60
26,70
7,20
8,60
3,60
6,10
8,46
9,40
7,40
7,10
3,70
6,10
4,70
6,20
0,27
0,67
1,05
0,47
0,56
0,40
0,76
3,70
1,10
0,53
0,41
0,38
1,4850
1,7140
0,8280
0,9190
4,6400
3,5099
1,4550
1,3340
1,0370
2,2865
1,0609
0,6765
1535
1564
1521,5
1546,4
1597,9
1577
1541
1540
1515,6
1545,6
1512,4
1537,6
3,4036
1619
1,7140
0,9190
4,6400
1564
1546
1598
7,50
9,20
7,20
0,77
1,20
0,13
0,52
0,19
0,31
0,14
0,13
0,11
55,10
56,60
59,00
26,70
21,90
25,50
8,00
6,70
5,70
0,81
3,90
0,70
8,00
12,00
5,00
7,72
0,04
0,43
0,10
0,32
1,30
1,10
0,77
1,94
0,17
0,19
0,10
0,21
56,10
49,90
55,80
52,16
28,60
29,30
34,00
29,78
7,20
8,60
6,10
8,46
0,27
0,67
0,47
0,56
ao
2,8150
4,1400
2,4140
5,1205
3.6064
2,5326
3,0263
3,4036
2,0369
3,1259
Temp
1610
1596
1625
1639
1610
1606
1597
1626
1619
1578
1609
51
%Ni
%Al
%Ti
%Ca
%Mg
0,23
0,26
0,10
0,32
0,18
0,09
0,10
0,12
0,07
0,13
0,17
0,13
0,162
0,215
0,236
0,175
0,245
0,180
0,257
0,002
0,198
0,277
0,186
0,052
0,0004
0,0002
0,0002
0,0001
0,0003
0,0003
0,0005
0,0001
0,0003
0,0004
0,0005
0,0001
0,00008
0,00017
0,00005
0,00045
0,00013
0,00031
0,00005
0,00292
0,00012
0,00339
0,00018
0,00049
0,00003
0,00011
0,00003
0,00006
0,00005
0,00004
0,00003
0,00037
0,00003
0,00025
0,00003
0,00010
0,22
0,27
0,10
0,32
0,18
0,10
0,10
0,13
0,07
0,13
0,16
0,13
0,027
0,004
0,044
0,030
0,015
0,033
0,056
0,065
0,063
0,045
0,062
0,050
0,0004
0,0003
0,0002
0,0003
0,0003
0,0002
0,0006
0,0005
0,0003
0,0004
0,0006
0,0004
0,00019
0,00024
0,00016
0,00021
0,00019
0,00023
0,00019
0,00019
0,00016
0,00017
0,00023
0,00017
0,00006
0,00005
0,00003
0,00004
0,00003
0,00009
0,00006
0,00012
0,00006
0,00004
0,00011
0,00005
0,22
0,27
0,10
0,32
0,00
0,11
0,10
0,13
0,08
0,13
0,17
0,13
0,024
0,004
0,019
0,014
0
0,026
0,105
0,068
0,050
0,033
0,064
0,042
52
Heat
%C
%Si
%Mn
Sample Before Degassing
1
0,36
0,29
0,30
2
0,17
0,27
0,62
3
0,09
0,22
0,22
4
0,11
0,20
1,18
5
0,12
0,12
0,85
6
0,14
0,20
1,14
7
0,42
0,27
0,32
8
0,76
0,34
0,65
9
0,15
0,20
0,28
10
0,28
0,25
0,65
11
0,50
0,28
0,30
12
0,34
0,29
0,28
Sample after Degassing
1
0,91
0,31
0,31
2
0,22
0,25
0,70
3
0,92
0,25
0,22
4
0,13
0,22
1,21
5
0,17
0,11
0,87
6
0,15
0,19
1,15
7
0,96
0,28
0,33
8
0,98
0,34
0,65
9
0,90
0,22
0,29
10
0,92
0,26
0,67
11
0,97
0,29
0,30
12
0,93
0,30
0,29
Final sample
1
0,94
0,30
0,31
2
0,22
0,25
0,70
3
0,93
0,31
0,22
4
0,15
0,25
1,20
5
0,20
0,11
0,87
6
0,15
0,20
1,17
7
0,97
0,27
0,32
8
0,99
0,34
0,65
9
0,95
0,21
0,31
10
0,94
0,26
0,67
11
0,97
0,28
0,29
12
0,93
0,31
0,30
%S
%Cr
%Ni
%Al
%Ti
%Ca
%Mg
0,025
0,036
0,012
0,013
0,037
0,040
0,016
0,013
0,011
0,013
0,013
0,017
1,7
1,14
1,45
2,03
0,51
1,02
1,42
1,68
1,46
1,7
1,4
1,72
0,22
3,55
0,10
0,48
0,18
0,15
0,10
0,13
0,08
0,13
0,17
0,14
0,056
0,034
0,144
0,081
0,051
0,045
0,057
0,057
0,079
0,053
0,057
0,033
0,0005
0,0005
0,0003
0,0004
0,0004
0,0005
0,0011
0,0013
0,0003
0,0009
0,001
0,0008
0,00020
0,00023
0,00020
0,00021
0,00020
0,00020
0,00025
0,00022
0,00017
0,00019
0,00022
0,00020
0,00017
0,00009
0,00011
0,00009
0,00005
0,00011
0,00020
0,00024
0,00013
0,00013
0,00016
0,00023
0,013
0,023
0,001
0,001
0,016
0,013
0,011
0,007
0,004
0,005
0,010
0,007
1,67
1,25
1,44
2,11
0,52
1,03
1,42
1,67
1,47
1,71
1,4
1,7
0,22
3,66
0,10
0,48
0,18
0,14
0,10
0,13
0,08
0,13
0,17
0,14
0,044
0,033
0,081
0,020
0,026
0,022
0,045
0,041
0,052
0,032
0,048
0,025
0,001
0,0005
0,0009
0,0007
0,0005
0,0006
0,0014
0,0014
0,0007
0,0013
0,0014
0,0013
0,00023
0,00020
0,00017
0,00027
0,00024
0,00029
0,00022
0,00023
0,00021
0,00024
0,00020
0,00025
0,00031
0,00018
0,00029
0,00027
0,00012
0,00020
0,00025
0,00038
0,00018
0,00029
0,00019
0,00029
0,010
0,022
0,001
0,001
0,020
0,022
0,010
0,006
0,007
0,006
0,008
0,006
1,68
1,25
1,44
2,15
0,52
1,03
1,41
1,67
1,47
1,71
1,39
1,7
0,22
3,65
0,10
0,48
0,18
0,15
0,10
0,13
0,08
0,13
0,17
0,14
0,037
0,029
0,076
0,028
0,027
0,030
0,043
0,041
0,044
0,029
0,042
0,034
0,0009
0,0005
0,0009
0,0005
0,0005
0,0006
0,0013
0,0014
0,0006
0,0013
0,001
0,0013
0,00025
0,00020
0,00119
0,00255
0,00019
0,00023
0,00024
0,00022
0,00020
0,00025
0,00023
0,00027
0,00031
0,00019
0,00045
0,00047
0,00011
0,00019
0,00019
0,00033
0,00018
0,00032
0,00017
0,00033
Si
Mn
Cr
Mo
Al
es
0,110
0,0630
-0,026
0,290
-0,028
-0,011
0,003
0,035
e Al
0,091
0,0056
0,000
0,000
0,030
0,000
0,000
0,045
Cu
Sn
Ti
Ca
Co
es
-0,0008
-0,016
-0,004
-0,072
0,01
0,000
0,003
0,0000
0,000
0,000
0,000
0,00
-0,047
0,000
e Al
53
20
%SiO2
15
10
0
0
3
4
Process Stage
Heat 1
Heat 2
Heat 3
Heat 4
Heat 5
Heat 6
Heat 7
Heat 8
Heat 9
Heat 10
Heat 11
Heat 12
7
6
%MnO
5
4
3
2
1
0
0
3
4
Process Stage
Heat 1
Heat 2
Heat 3
Heat 4
Heat 5
Heat 6
Heat 7
Heat 8
Heat 9
Heat 10
Heat 11
Heat 12
54
%CaO
50
40
30
1-Sample in EAF b efore Tapping
2-Sample at tapping
3-Sample b efore slag removal
4-Synthetic slag
5-Sample b efore degasing
6-Sample after Degassing
7-Sample at completion of refining
20
10
0
0
4
Process Stage
Heat 1
Heat 2
Heat 3
Heat 4
Heat 5
Heat 6
Heat 7
Heat 8
Heat 9
Heat 10
Heat 11
Heat 12
%Al 2O3
25
20
15
1-Sample in EAF b efore Tapping
2-Sample at tapping
3-Sample b efore slag removal
4-Synthetic slag
5-Sample b efore degasing
6-Sample after Degassing
7-Sample at completion of refining
10
5
0
0
Process Stage
Heat 1
Heat 2
Heat 3
Heat 4
Heat 5
Heat 6
Heat 7
Heat 8
Heat 9
Heat 10
Heat 11
Heat 12
55
25
%MgO
20
15
10
0
0
3
4
Process Stage
Heat 1
Heat 2
Heat 3
Heat 4
Heat 5
Heat 6
Heat 7
Heat 8
Heat 9
Heat 10
Heat 11
Heat 12
%FeO
20
15
10
0
0
3
4
Process Stage
Heat 1
Heat 2
Heat 3
Heat 4
Heat 5
Heat 6
Heat 7
Heat 8
Heat 9
Heat 10
Heat 11
Heat 12
56
Si
0,25
14,42
0,25
Mn
0,23
457,30
0,65
S
0,02
0,10
0,01
Ti
0,0003
0,0000
0,0009
Ca
0,0002
0,0000
0,0002
Al
0,03
36,74
0,05
Mg
0,00004
0,00000
0,00013
-7,67
-23,90
-1,73
0,6184
0,0150
-15,51
0,09262
SiO2
2,77
22,05
9,20
85,73
63,67
29,77
MnO
0,14
1,10
1,20
11,18
10,08
7,81
S
0,05
0,36
0,19
1,77
1,41
1,41
TiO2
0,1127
0,8961
0,1300
1,2114
0,3153
0,1890
CaO
66,34
527,42
56,60
527,42
0,00
0,00
Al2O3
22,70
180,49
21,90
204,07
23,59
12,49
MgO
4,46
35,45
6,70
62,43
26,99
16,27
FeO
0,66
5,25
3,90
36,34
31,10
24,18
22,10
-16,09
-0,32
0,8074
0,02
-3,02
16,37
Mass of Top slag = Mass of CaO in sythetic slag / % Cao before degassing = 931.84Kg
Extra slag = Mass of Top slag before degassing - Mass of synthetic slag = 136,84kg
Degassing
Steelanalysis before degassing[%]
Extra alloying [kg]
Steel analysis after degassing [%]
Mass difference ('amt after' - 'Amt
Before' - 'Alloy addition') [kg]
Slaganalysis before degassing [%]
Weight before degassing [kg]
Extra slag addition [kg]
Slag analysis after degassing [%]
Weight after degassing [kg]
Mass difference in slag [kg]
Equivalent element in slag [kg]
Elemental Sum in slag&steel
Final sample
Si
0,25
0,00
0,26
Mn
0,65
0,00
0,67
S
0,01
4,37
0,01
Ti
0,0009
0,0000
0,0013
Ca
0,0002
0,0000
0,0002
Al
0,05
0,00
0,03
Mg
0,00013
0,14800
0,00029
14,56
SiO2
9,20
85,73
0,00
8,70
81,36
-4,37
-2,04
31,66
MnO
1,20
11,18
0,00
0,09
0,84
-10,34
-8,01
-12,42
S
0,19
1,77
0,00
1,20
11,22
9,45
9,45
0,4288
TiO2
0,1300
1,2114
0,0000
0,1700
1,5897
0,3784
0,2268
0,0549
CaO
56,60
527,42
0,00
56,40
527,42
0,00
0,00
-20,82
Al2O3
21,90
204,07
0,00
28,30
264,65
60,57
32,07
0,01964
MgO
6,70
62,43
0,00
6,10
57,04
-5,39
-3,25
FeO
3,90
36,34
0,00
0,53
4,96
-31,39
-24,40
12,52
23,65
-2,97
0,6556
0,05
11,25
-3,23
Mass of Top slag = Mass of CaO before degassing / % Cao after degassing = 935,14Kg
Extraslag=Mass of Topslag after degassing - Mass of Topslag before degassing=3,30kg
Si
Mn
S
Ti
Ca
Al
Mg
0,26
0,00
0,67
0,00
0,005
0,09
0,0013
0,00
0,0002
0,00
0,032
0,00
0,00029
0,00
0,26
0,67
0,006
0,0013
0,0003
0,029
0,00032
0,00
0,00
0,94
0,0000
0,0103
-3,10
0,03102
57
Appendix XI: Model for predicting ao activity for online process using existing process data
1000
ao (ppm)
100
10
0,1
1500
1550
1600
1650
1700
1750
Temp (C)
0,002-0,004%Al
0,008-0,019
0,020-0,030
0,031-0,049
0,050-0,069
>0,069
Calculated
Heats
1
2
3
4
5
6
7
8
9
10
11
12
Ohta&suito
2,67E-05
6,85E-05
3,16E-06
1,86E-05
3,84E-05
4,33E-05
1,17E-05
2,07E-05
1,56E-05
4,06E-05
1,65E-05
3,64E-05
Al2O3 =1
2,32E-04
2,94E-04
1,64E-04
1,28E-04
4,05E-04
3,00E-04
2,16E-04
1,90E-04
2,29E-04
2,58E-04
1,46E-04
3,26E-04
Data
2,75E-04
2,44E-04
2,84E-04
1,59E-04
3,95E-04
2,89E-04
2,61E-04
2,34E-04
2,91E-04
2,93E-04
1,84E-04
2,85E-04
ao
2,82E-04
4,14E-04
2,41E-04
1,59E-04
5,12E-04
3,61E-04
2,53E-04
3,22E-04
3,03E-04
3,40E-04
2,04E-04
3,13E-04
58
Ohta&suito
2,69E-04
5,76E-04
9,65E-05
2,10E-04
3,39E-04
3,55E-04
1,59E-04
2,25E-04
1,88E-04
3,71E-04
1,95E-04
3,40E-04
Al2O3=1
2,97E-04
3,78E-04
2,36E-04
2,52E-04
5,21E-04
3,85E-04
2,76E-04
2,43E-04
2,94E-04
3,30E-04
1,86E-04
4,18E-04
Measured
Data
3,52E-04
2,89E-04
3,70E-04
1,19E-04
5,94E-04
3,80E-04
3,25E-04
2,69E-04
3,85E-04
3,88E-04
1,70E-04
3,73E-04
ao
2,82E-04
4,14E-04
2,41E-04
1,59E-04
5,12E-04
3,61E-04
2,53E-04
3,22E-04
3,03E-04
3,40E-04
2,04E-04
3,13E-04
Calculated Ls
Heats
1
2
3
4
5
6
7
8
9
10
11
12
Ohta&suito
4498
671
71815
10917
3890
1818
14948
3424
25155
3207
5893
2901
Al2O3=1
517
156
1161
1030
348
263
810
373
1711
505
666
324
Measured
Meas. ao
426
111
1434
885
275
218
690
220
1297
383
478
338
Ls
130
48
970
750
121
185
118
186
188
240
91
300
59
Ohta&suito
0,005
0,020
0,001
0,001
0,009
0,014
0,002
0,005
0,001
0,004
0,003
0,006
Al2O3=1
0,005
0,018
0,001
0,001
0,012
0,015
0,003
0,005
0,001
0,003
0,003
0,007
Measured
Meas
ao
0,005
0,019
0,001
0,001
0,012
0,014
0,003
0,006
0,001
0,004
0,003
0,006
[%S]f
0,010
0,023
0,001
0,001
0,016
0,013
0,010
0,006
0,004
0,005
0,008
0,007
60