Electrometallurgy and Ferroalloys Production
Electrometallurgy and Ferroalloys Production
Electrometallurgy and Ferroalloys Production
Ostrava 2014
Description: ELECTROMETALLURGY AND FERROALLOYS PRODUCTION
Author: Karel Michalek
Academic materials for the Metallurgy engineering study programme at the Faculty of
Metallurgy and Materials Engineering.
Proofreading: none.
Project designation:
Operation Programme of Education towards Competitive Strength
Description: ModIn - Modular innovation of bachelor and subsequent master programmes at
the Faculty of Metallurgy and Materials Engineering of VB - TU Ostrava
Ref. No.: CZ.1.07/2.2.00/28.0304
Realisation: VB Technical University of Ostrava
Karel Michalek
VB Technical University of Ostrava
Electrometallurgy and Ferroalloys Production
1
Electrometallurgy and Ferroalloys Production
13. Production of steel in induction furnaces. The principle of heating and melting.
Construction design of the induction furnaces. The basic electrical characteristics
of an induction furnace. Technology of steel production in induction furnaces.
Vacuum induction furnaces. Metallurgical processes in the vacuum.
The electrical slag remelting.
14. The basics of thermodynamics of ferroalloys production. Carbothermical,
silicothermical and aluminothermical methods of ferroalloys production.
The production of main types of ferroalloys: FeMn, FeCr, FeSi, FeTi, FeW.
2
Electrometallurgy and Ferroalloys Production
PREFACE
Study support to the subject Electrometallurgy and Ferroalloys Production
is primarily intended for students of combined studies. In the combined form of study,
there is a much smaller proportion of direct contact teaching, which makes this study
much more difficult for students. Our study support to the subject Electrometallurgy
and Ferroalloys Production can help you to eliminate this handicap to a certain
extent. These is not a new textbook, there are enough of those. The study support is
a replacement, if possible, for the lack of direct instruction and interlink to a
subsequent study of professional literature itself, whether it be textbooks or other
publications.
When writing this support I have tried to maximize the clarity of the text. This
cannot be achieved, at least in my opinion, without some simplification, reduction and
sometimes even inaccuracy. If someone feels that simplification is too much, I
apologize in advance. But my experiences in teaching this subject led me to a result
which is just this text.
Despite careful checking of the text, it is almost certain that I did not avoid
errors, typing errors, etc., maybe even factual mistakes. I will be most grateful, if you
notify me about them so I can gradually correct them. You can notify me either
directly during classwork or by email to [email protected]
I wish all of you who will use this study support, a lot of strength in your study!
3
Electrometallurgy and Ferroalloys Production
THEMATIC BLOCK 1
4
Electrometallurgy and Ferroalloys Production
The heat is created by the flow of electric current through the resistive elements
(silites sintered silicon carbides SiC, molybdenum disilicid MoSi2, Tungsten
heating elements, graphite heating segments, etc.
These furnaces are used most often to heat the metal before its heat
processing or they are used as drying or baking furnaces, but also for melting
color metals and alloys as well as for research purposes in laboratory
conditions (Tammanns furnace), etc.
5
Electrometallurgy and Ferroalloys Production
6
Electrometallurgy and Ferroalloys Production
Questions
1. The present share of steel production in EAF, the state in EU, in the whole
world, in CR, current technical parameters of EAF.
2. The division of electric furnaces.
3. Principle of heating in the resistance furnaces, use of resistance furnaces.
4. Fundamentals of high power alternating current circuit with an ohmic
resistance, with inductance, with capacity (see Appendix).
5. Fundamentals of high power electrotechnics of alternating current series
and parallel resonance, resonant frequency (see Appendix).
6. Fundamentals of high power electrotechnics of alternating current the power
of alternating current (see Appendix).
7
Electrometallurgy and Ferroalloys Production
THEMATIC BLOCK 2
8
Electrometallurgy and Ferroalloys Production
S,O
Ui lo lo
k
- the voltage drop upon the flow of the current through the cathode and anode
area of conductive discharge (between the cathode and the columns of the
arc and the column of the arc and the anode)
The values of for different environments:
graphite molten steel 22 V
graphite alkaline slag 9 V (Ca is easily ionisable)
graphite acid slag 30 V
S,0 - resistivity of the arc column; m
k - constant of proportionality; m2A-1
- gradient of the electrical potential in the arc column; V.m -1 of the arc
The degree of ionization of the mixture of vapors and gasses forming the arc
column has a strong influence over the value of . The higher this degree of
ionization, the lower the value of . The degree of ionization increases with the
temperature.
The values of during the individual phases of melting:
melting 10000 12000 V/m of the arc (10 - 12 V/mm)
oxidation phase 3500 4000 V/m of the arc (3.5 4 V/mm)
reduction phase 1000 1200 V/m of the arc (1.0 1.2 V/mm)
lo length of the arc
The influence of the shape of the electrode end on the length of the arc only in
short arcs it is the distance electrode-pool
9
Electrometallurgy and Ferroalloys Production
At very high current intensities, the voltage on the arc may decrease under the
value of Ui, and the arc then becomes unstable leading to its extinction that is
why the stabilization is necessary.
10
Electrometallurgy and Ferroalloys Production
In other words:
UO = Usource - UR = Usource - R . I
The equation can be solved visually by drawing the arc characteristics and the so-
called difference line Usource - UR. The intersections of difference lines with the arc
characteristic determine the current-voltage ratios at which the arc can exist. If the
intersection does not exist, the arc cannot burn in a stable way.
At points A and B, the conditions for arc burning are met. Stable arc burning is
possible only at point B. The burning at point A is unstable and the arc moves
towards the point B, towards higher current intensities at lower voltage.
11
Electrometallurgy and Ferroalloys Production
The arc burning at point C occurs on the boundary of stability for example when
the value of R is high and there is a big decay of voltage on the arc, meaning that the
voltage on the arc is not very different from the initial voltage. With further increase of
R the voltage on the electrodes after igniting the arc decreases under the initial
voltage the arc goes out or it is not even created, meaning that
UO > Usource - UR
On the other hand, at low values of R (the difference line crosses the x axis at higher
values of current) the arc burning is moved towards the extreme currents, which can
lead to the destruction of electrodes if the source is hard enough.
If the current changes depending on the time, the arc voltage does not follow the
static characteristic, but it moves along the dynamic characteristic.
In order for the direct current arc to burn in a stable way, there must be an
intersection of the difference line with the arc characteristic. This can be achieved by
the following methods:
12
Electrometallurgy and Ferroalloys Production
13
Electrometallurgy and Ferroalloys Production
The consequence of intermittent arc burning reducing the average active power
released by the arc.
The alternating of the function of cathode and anode impairment of thermal
emission of electrons from the cold batch at the beginning of the melting, there is
an asymmetry in the current load, which leads to instability in arc burning and its
extinction.
14
Electrometallurgy and Ferroalloys Production
15
Electrometallurgy and Ferroalloys Production
Questions
16
Electrometallurgy and Ferroalloys Production
THEMATIC BLOCK 3
where: Pinput power fed into the working area of the furnace
Poutput power off from from the working area of the furnace
The mentioned relations show that the increase of the values of Puseful can be
achieved by increasing Pel a Pex and by decreasing Plos a Plining
17
Electrometallurgy and Ferroalloys Production
For the rational energy management regime, it is neccessary to reach the optimum
value of power brought to the working area of the furnace.
18
Electrometallurgy and Ferroalloys Production
19
Electrometallurgy and Ferroalloys Production
The I2 current can be determined using the relation including the impedance of the
circuit Z
U 2,p U 2,p
I2
Z R R 0 2 X 2L
The power factor cos can be determined using the ratio of the resistance and
impedance of the circuit
R R0 R R0
cos
Z R R0 2 X L2
The decisive part of the value of Pel is formed by the power input, which is
released by the arcs themselves:
Po Pel
The resulting relation for the power released on the arcs is:
20
Electrometallurgy and Ferroalloys Production
21
Electrometallurgy and Ferroalloys Production
During a short-circuit the Ro is zero, but the ohmic resistance R remains. That
is why Ptotal,el does not decrease under zero, but to a certain real value (the electrode
is heated by ohmic heat). Po is zero, however, because the arc does not burn.
22
Electrometallurgy and Ferroalloys Production
P0
e
Ptotal,el
Operating the EAF on the ascending part of the performance curve of the arc
longer arcs, lower currents, higher power factor, greater stress of the lining.
Operating the EAF on the descending part of the performance curve of the arc
shorter arc, higher currents, lower power factor, lesser stress of the lining, higher
requirements on the transformer.
23
Electrometallurgy and Ferroalloys Production
Consequence:
Bulging of the arcs towards the walls of the furnace increasing the thermal
stress on the furnace walls
Existence of axial forces in the arc recess of the arc, creating a wall
24
Electrometallurgy and Ferroalloys Production
Transition of hydrogen and nitrogen to the molten pool with the condition
of dissociation of gas molecules to atoms (arc)
Formation of calcium carbide carbide slag
(CaO) + 3 Cs (CaC2) + COg strongly endothermic reaction
Carburizing of the pool from the electrodes (electrode breaking,
improper regulation of the electrodes etc.)
Evaporation of the pool ingredients Ni, Mn (due to the high vapor
pressure of metals)
25
Electrometallurgy and Ferroalloys Production
regular productivity RP
high productivity HP
ultra high productivity UHP
super ultra high productivity SUHP
Criteria of UHP:
1. The maximum value of specific active electrical power input Ptotal,el during the
period of melting (Ptotal,el=Papparent . cos) must reach 300-600 kW/t of the liquid
metal (in other words Papparent of the transformer of app. 500 -1000 kVA/t).
Up to 35 t 40 90 t 100 t
RP furnaces 200 350 150 300 150 - 250 kW.t -1
UHP furnaces 450 550 400 500 300 400 kW.t -1
SUHP furnaces 600 - 700 550 - 600 500 550 kW.t -1
2. The ratio of average power input of the operating furnace to the maximum
electrical power input during the melting must be 0,7
3. The ration of arc burning period to the total length of the melting has to be 0,7
4. High durability of the lining
5. Uniform distribution of the received energy between individual phases
26
Electrometallurgy and Ferroalloys Production
high input of chemical energy. The weight of the melting in these furnaces is up to
300 t, the diameter of the hearth up to 9m, their productivity may be up to 2 million
tons/year, the melting period according to the technology used from 30 to 45
minutes.
Questions
27
Electrometallurgy and Ferroalloys Production
1. Electrical and thermal working mode of the electric arc furnace how to
influence the useful power put into the EAF.
2. A substitute diagram of one phase EAF.
3. How is it possible to perform the change of power released on the arcs.
4. The combined working characteristic of the EAF - construction.
5. The work of EAF on the increasing and decreasing branch of the characteristic,
advantages and disadvantages.
6. Specific consumption of electric energy during the melting in EAF.
7. Dynamic, physical and chemical effects of arcs in the EAF.
8. UHP and SUHP furnace, conditions of including EAF among the UHP furnaces
and UHCP furnaces.
28
Electrometallurgy and Ferroalloys Production
THEMATIC BLOCK 4
29
Electrometallurgy and Ferroalloys Production
Real values of the thermal effect achieved in melting in EAF are between
2 and 4,5 kWh/1 m3 of O2
Advantages of the occurrence of exothermic reactions in the melt:
the forming heat completely moves into the batch (melt)
large amount of CO forms, which represents additional - and in terms of potential
thermal effect even more significant - source of energy (thermal effect of the
carbon oxidation reaction until the formation of CO2 is triple compared to the
oxidation into CO only).
30
Electrometallurgy and Ferroalloys Production
31
Electrometallurgy and Ferroalloys Production
Oxygen-powered burner
JetBOx (Air Products) with
the influx of powdered
carbide substances
Oxygen-powered burner
JetBOx (Air Products) with
the influx of powdered
carbide substances
32
Electrometallurgy and Ferroalloys Production
34
Electrometallurgy and Ferroalloys Production
Foaming nozzles
Blowing oxygen + ground carbide substances (coke, coal) into the slag
Reaction of carbon and blown oxygen in the slag with the creation of CO bubbles
causing the slag foam. Possible course of the reaction of carbon with iron oxides in
the slag.
Formation of CO bubbles, formation of foaming slag shielding of long arcs.
Advantages to using a foaming slag:
decreases the use of lining and electrodes
decreases thermal loses through the furnace walls
better transfer of heat from the arc into the pool
decreases the furnace noise - the arc is shielded
35
Electrometallurgy and Ferroalloys Production
Basic methods of placing the stirring blocks in the bottom of the EAF
hearth
hearth with
EBT
36
Electrometallurgy and Ferroalloys Production
37
Electrometallurgy and Ferroalloys Production
38
Electrometallurgy and Ferroalloys Production
EAF productibility
EAF productibility is usually given in tons of produced steel in 24 hours and is one of
the main parameters of an EAF.
where:
G- furnace productibility; t/24 h
go - mass of the melting; t
n- number of meltings performed in 24 hours
celk - overall time of melting; h
1 - length of the time interval since turning off the furnace during tapping
until turning on the furnace for the next melting; h
2 - length of the melting period
where 2 = '2 + ''2
'2 - the sum of period when the arc is interrupted
''2 - the sum of periods when the arc is ignited
3 - the time of the period of finishing a heat
39
Electrometallurgy and Ferroalloys Production
1
In period 1 the transformer is not under load - it is turned off. This intervals
length depends on the work organization, difficulty and scale (or length) of inter-
melting repairs, development of contracts, etc.
'2
Interruption of the arc during the melting period is always undesirable and is
caused by various factors. Most often is it wrongly assembled batch that can
disintegrate onto the electrodes causing short circuits, etc. To prevent the arc being
switched off, it is necessary to include choke into the circuit (lowering the cos).
Interruption of the arc burning is related to the possibilities of the transformer, which
does not allow for switching to other voltage level under load. The value of '2 is
influenced by the perfection of electrical and mechanical equipment of the furnace
(parameters of electrode regulation, etc.).
''2
Shortening the period when the arc is ignited can be done only under the
assumption of further intensification of the melting - is the funcion of Puseful, which is
dependent on the power lead into the EAF (UHP furnace, oxygen-powered burners,
etc.) and on the power lead out (especially thermal losses - perfect isolation of the
furnace coating). Some furnace constructions utilize water-cooling with large-area
coolers (i.e. higher outflow of heat - losses). In such case, assumptions must be
made to increase Pel (active power of electrical energies) or Pex (power by exothermic
reactions), so that the shortening of ''2 occurs.
3
During the finishing period, the transformer is not under full load. The length of
this period is determined primarily by the technology used - production program,
furnace equipment, scale of the out-of-furnace processing of steel in the steel-mill,
etc.
40
Electrometallurgy and Ferroalloys Production
Questions
41
Electrometallurgy and Ferroalloys Production
THEMATIC BLOCK 5
42
Electrometallurgy and Ferroalloys Production
43
Electrometallurgy and Ferroalloys Production
45
Electrometallurgy and Ferroalloys Production
46
Electrometallurgy and Ferroalloys Production
The furnace transformer lowers the high voltage from the supply grid (6 30 kV) to
the voltage suitable for powering the EAF (100 1000 V)
160 V 93 V
(se k )
47
Electrometallurgy and Ferroalloys Production
EAF choke
The choke balances (lowers, limits) sharp changes of the current in the electrical
circuit of EAF, which form for example at turning the circuit on/off, short circuits, etc.
Changes in the electrical circuit cause a change in the magnetic field around the coil
and then electro-motoric voltage is induced in the coil, which acts always against
changes that have caused it.
It is connected in a series to the primary side of the furnace transformer.
Construction - similar to the transformer, the choke has one coil; the magnetic circuit
is not closed - increase of the magnetic flow deviation - increase of inductivity. It has
minimal ohmic resistance.
48
Electrometallurgy and Ferroalloys Production
49
Electrometallurgy and Ferroalloys Production
Melting the batch: to increase the effect from 0,7 or 0,8 to 0,9, it is necessary to
compensate reactive energy by 2,6 to 4,5 MVAr (A-A, B-B).
Oxidation period of melting: works with lower power in the transformer and with
worse power factor (point C) for achieving cos =0,90 it is necessary to compensate
by 4,5 MVAr (C-C).
Finishing the melting: the transformer is under 25 % load (point D) with power factor
of 0,65, therefore it is necessary to compensate by 1,2 MVAr (D-D).
50
Electrometallurgy and Ferroalloys Production
Electrical lead between the outputs on the secondary side of the transformer and the
furnace workspace - copper flanges, flexible cables, conductors on the electrode
holders, electrode holders, electrodes including the links.
51
Electrometallurgy and Ferroalloys Production
secondary side
of transformer electrodes of EAF
52
Electrometallurgy and Ferroalloys Production
EAF electrodes
Price of the electrodes - cca 40.000 CZK/1t for RP and HP, up to 100.000 CZK /1t for
a UHP
Graphite electrodes are usually used in EAFs.
Influence of temperature on
the change of thermal
100 conductivity and resistivity
of graphite electrodes
0 1000 2000 C
54
Electrometallurgy and Ferroalloys Production
55
Electrometallurgy and Ferroalloys Production
56
Electrometallurgy and Ferroalloys Production
Questions
57
Electrometallurgy and Ferroalloys Production
THEMATIC BLOCK 6
Apart from this, other requirements are put on the automatic regulation
ensure conditions for the arc ignition
exiting of electrodes or unplugging the furnace from the grid in case of the batch
sliding and short circuit occurrence
to prevent carbonization of the pool from electrodes during the reduction period
systems of regulation of each electrode cannot be mutually influenced
it must react even to non-standard working conditions, such as presence of non-
conductive material in the batch
it must allow for manual control over electrodes - especially their exit from the
furnace
Power of the arc can be regulated by changing its length - shortening will increase its
power (increasing branch characteristic).
The working point cannot be determined by power because the same power can be
achieved at two different values of voltage - the power cannot be used as a regulated
quantity.
58
Electrometallurgy and Ferroalloys Production
Division of regulation:
non-proportional speed of electrode movement in not dependent on the size
of regulated quantity deviation (e.g. contact regulation)
proportional speed of electrode movement in dependent on the size of
regulated quantity deviation (e.g. hydraulic regulator)
Insensitivity range - electrode does not react to the change of regulated quantity
deviation
59
Electrometallurgy and Ferroalloys Production
Time progress of electrode speed from since the start of the given regulatory
deviation until its removal
The regulator will have faster feedback if the overall delay tz is lower and if the time
constants n and d are lower. The size of the time constant is positively influenced by
the speed of electrode movement.
60
Electrometallurgy and Ferroalloys Production
61
Electrometallurgy and Ferroalloys Production
Both coils affect the rocker system of the relay. If the current of the arc increases, the
rocker falls out of balance and switches a set of contacts of the electromotor, which
lifts the electrode through a pulley system. If the current in the electrode decreases,
the balance relay switches the contacts to move the electrode downward.
62
Electrometallurgy and Ferroalloys Production
The core element of this type of regulation is the so called Ferraris engine, its rotor is
in the shape of aluminum drum and the stator has two-phase coils - excitation coil
and regulatory coil.
The excitation coil is powered by the voltage from other two phases other than the
regulated phase. The regulation coil is differentially connected to two sources of
alternating voltage. One of them is the voltage proportional to the voltage between
the electrode and the batch. The other source is the voltage which is excited by the
flow of regulated phase in the measuring transformer. If these two voltages are of
same amplitudes, no current flows through the regulatory coil, because both sources
have opposite effect (phase shift is 180). If a difference is formed - such as during
the increase of the arc current related to the decrease of voltage on the electrode -
some current flows through the regulatory coil which creates rotary electromagnetic
field; its effect speeds up the rotor. The torque is proportional to the current flowing
through the regulatory coil, the direction of rotation is dependent on if the balance is
disrupted by overflow of voltage which is proportional to the arc current over the
voltage measured from the electrode or vice-versa. It is clear that the regulated
quantity is the arc impedance. The rotor here acts as the core element of the
regulator. Rotation of the rotor is transferred through the gear segment and an arm
onto the rod of the regulatory hydraulic valve damper, which controls the hydraulic
piston with the arm of the electrode.
63
Electrometallurgy and Ferroalloys Production
64
Electrometallurgy and Ferroalloys Production
Gradient of voltage on the arc (V.mm-1) changes depending on the batch composition
and temperature during the technological process more than by an order, i.e.
Electrical parameters of individual arcs are mutually bound because the electrical
circuit for the current of the given arc must necessarily close through arcs of the
remaining electrodes, which means that
in the situation of a given electrode, the arc length corresponds to the required state
and it is not suitable to move the electrode, especially the change of current in a
different electrode (albeit short-term) will be seen as a change of current. It is evident
that if the change is short term, it would be best not to react to it at all.
65
Electrometallurgy and Ferroalloys Production
electromagnetic coil for induction mixing is placed under the bottom of the arc
furnace (analogy to the expanded stator of an asynchronous engine)
rotor ( with the short-term anchor) is the pool itself
the coil is wired by current of lower frequency (up to 1 Hz).
the coating on the furnace floor must be made from non-magnetic steel
the source of the connecting current are rotation or thyristor converters
If a current of low frequency passes through the coil, it causes movement of the melt
as shown on the figure below.
66
Electrometallurgy and Ferroalloys Production
EAF linings
Dry floors provide several advantages - they do not have to be dried, they
exhibit higher density and volumetric stability. Before the first melting, the floor is
covered by pieces of sheet metal and lighter waste is set. The first melting is
performed intermittently at lower degrees of voltage.
In the production of stainless steels through oxidation remelting, the floors are
strained by significantly high temperatures. Suitable lifetime of floors has been
achieved through several preventive measures that result in formation of a chromium
gathering at the place where hearth meets the pool.
The gathering is formed during the processes between the original magnesite
or dolomite hearth and the elements of chromium slag, components of highly-alloyed
pool and the used reparatory material. The main components of this gathering are
complex spinels of MgO.Cr2O3, FeO.Cr2O3.
Furnace walls
The furnace wall lining is also strained by temperature changes due to arc
burning, mechanical tension during the tilting of the furnace and other factors.
The finish of the EAF walls and their lining can be divided into 2 groups based
on the method of heat transfer from the workspace of the furnace:
outflow of the heat through the furnace coating into its surrounding where the
magnesite lining itself is isolated from the coating to varying degree
The use of water coolers (for large areas) which remove the heat from larger part
of the furnace workspace, which is made up by a thin lining or coating of ceramic
67
Electrometallurgy and Ferroalloys Production
matter or gatherings on the colder ones. The use of coolers allows for full use of
the UHP furnaces and thus higher productivity, lower consumption of heat-
resistant material.
Water cooled panels are constructed as tubular (the radius of the tubes is 70-
90 mm), the thickness of the wall is 8-10mm and it must be sufficiently resistant to
mechanical influences on the other hand it must ensure fast transfer of heat into
the cooling water. They are made from steel with good thermal conductivity
(50 Wm-1K-1) or for especially strained areas even from copper (383 Wm-1K-1)
such as for the zone near to the slag line or oxygen-burning burners, etc. The
panels do not come into long term direct contact with liquid metal or slag. They
are placed above the slag line.
68
Electrometallurgy and Ferroalloys Production
The roofs used to be lined by silica, because it has suitable properties - low
weight, not too expensive. But if the temperature only slightly exceeds 1670C, it lead
to a significant wear.
Modern EAFs use aluminum rich roofs, basic roofs or water cooled lids.
Aluminum-rich - based on Al2O3, 75-80 % Al2O3
Basic - magnesite-chromium
Water-cooled - the coolers are in the peripheral part, the middle part around the
electrode is built using masonry methods.
Coolers are built using a pipe-space-pipe system, the cooling is divided into several
cooling circuits. On the inside (furnace) side, the tube constructions are melted by
thorns, which act as holders of the refractory concrete that is put onto the entire
surface before the furnace is used. The weight of the water-cooled lid is small than
the brick one. The amount of flowing water must ensure sufficient cooling without the
formation of vapor - up to 200 m3/hour for a lid that is 6 m in diameter.
69
Electrometallurgy and Ferroalloys Production
The stated procedures may be combined to achieve the maximum effect and thus
reducing secondary emissions from the operation of arc furnaces.
70
Electrometallurgy and Ferroalloys Production
Component Dust from carbon and low- Dust from high-alloy and
alloy steel production, % stainless steel production, %
Adjustment of furnace gases suction consists primarily in their clean-up using bag
filters (90 % of devices) or using electrostatic separators or water filters. 2/3 of the
separated dust is dumped in the EU, the rest is recycled (dust from the production of
stainless steel) or is further utilized externally.
71
Electrometallurgy and Ferroalloys Production
INPUT OUTPUT
RAW PRODUCTS
MATERIALS
steel scrap kg/t 1080 -1130 liquid steel kg 1000 (yield
92,6-88,5%)
lime kg/t 30-80 EMISSION
coal kg/t 13-15 dust g/t 1-780
graphite kg/t 1,5-4,5 Hg mg/t 6-4470
electrodes
lining kg/t 1,9-25,1 (diam.8,1) Pb mg/t 16-3600
liquid melt kg/t Cr mg/t 8-2500
DRI kg/t Ni mg/t 1-1400
pig iron kg/t Zn mg/t 280-45600
Cd mg/t 1-72
Cu mg/t 1-460
ENERGY HF mg/t 700-4000
total energy MJ/t 2300-2700 HCl mg/t 800-9600
(630-750kWh/t)
electricity MJ/t 1250-1800 SO2 g/t 24-130
(350-520 kWh/t)
3
oxygen m /t 24-47 NOx g/t 120-240
CO g/t 740-3900
water closed cooling TOC g C/t 16-130
circuit
benzene mg/t 170-4400
chlorbenzenes mg/t 3-37
PAH mg/t 3,5-71
PCB mg/t 1,5-45
PCDD/F g I- 0,07-9
TEQ/t
slag from the Kg/t 100-150
furnace
slag from the Kg/t 10-30
ladle
dust Kg/t 10-20
refractory Kg/t 2-8
bricks
noise DB (A) 90-125
72
Electrometallurgy and Ferroalloys Production
Questions
73
Electrometallurgy and Ferroalloys Production
THEMATIC BLOCK 7
74
Electrometallurgy and Ferroalloys Production
Double-slag technology
Before the rise of secondary metallurgy, it was the most used one. It is currently used
in smaller units for creation of special steels.
75
Electrometallurgy and Ferroalloys Production
76
Electrometallurgy and Ferroalloys Production
Melting period
It is the time period from ignition of the arc until the withdrawal of the first sample
after melting.
Maximum value of secondary voltage is used for melting (longer arcs are shielded by
batch), which shortens the melting period.
Intensification of melting:
Blowing of gaseous oxygen - aids the melting of unmelted chunks of batch
outside of the electrode area
Use of oxygen-powered burners - usually for methane and oxygen, batch can be
preheated outside the furnace in setting baskets, shafts etc.
Rotary hearth - hearth will rotate by 30-40
The melting period ends with the complete melting of batch, the transformer is
switch to a lower level of secondary voltage (shorter arcs).
77
Electrometallurgy and Ferroalloys Production
78
Electrometallurgy and Ferroalloys Production
Molecular theory:
2 P + 5 (FeO) = (P2O5) + 5 Fe
(P2O5) + 4 (CaO) = (Ca4P2O9)
2 P + 5 (FeO) + 4 (CaO) = (Ca4P2O9) + 5 Fe
Ionic theory:
P + 4 (O2-) + 2,5 (Fe2+) = (PO43-) + 2,5 Fe
79
Electrometallurgy and Ferroalloys Production
Equilibrium constant
KC,O = pCO/ fC . C . fO . O
log KC,O = (1168/T) +2,07
G = 5343 9,47.T
The overall thermal effect of the carbon oxidation reaction in iron melt is formally
equal to the progress of the summary reaction
[C] +1/2 O2 = COg
The progress of carbon reaction is possible only after fulfilling all other conditions
(physical ones) - partial pressure of pCO in the forming bubble must be greater than
the sum of patm, pfer and pkap.
80
Electrometallurgy and Ferroalloys Production
81
Electrometallurgy and Ferroalloys Production
The time period since deoxidation of the pool until the tapping.
Deoxidation of steel
Diffusion deoxidation
Basis:
lowering the activity (FeO) in slag - by adding C, FeSi, FeMn
resulting in violating the equilibrium between the amount of oxygen in the
pool and slag and beginning the process of the extraction process
FeO (FeO)
LO
a FeO
( FeO )
LO
O
2
aO FeO resp.
O
With lowering of (FeO) or a(FeO) the violation of equilibrium occurs and also
subsequent transfer of oxygen from metal into slag until a new equilibrium is set:
(FeO) = Lo FeO
82
Electrometallurgy and Ferroalloys Production
a) White slag
White slag a mixture of lime and fluorspar (cca 4:1), after forming the liquid slag,
powdered coke or ground electrodes (sources of carbon are added).
A reaction occurs
83
Electrometallurgy and Ferroalloys Production
b) Carbide slag
Ration of coke in the reduction mixture is higher, in one dose contains only CaF2 and
CaO without FeSi. In high temperatures under the arcs, the following reaction occurs
two elements take part in slag deoxidation (Ca, C), which positively affects on greater
decrease of (FeO) content in the slag - down to 0,3-0,5 %. Content of CaC2 in
carbide slag is higher - 1 to 2,5 %.
Disadvantage
- possibility of carbonizing the pool
- higher density
- lower fluidity (higher viscosity)
- lower interphase tension between slag and steel (high wettability)
Due to the stated disadvantageous physical properties, carbide slag has difficulties
being released from the metal during tapping and may be the cause of a great
amount of non-metal inclusions in the steel. For these reasons, carbide slag is
transformed into white slag before tapping by ventilating the furnace (raising the lid),
surplus CaC2 undergoes oxidation and we put ground FeSi onto the slag..
By the end of the reduction period, we achieve content of oxygen in steel between
0,0400 to 0,0800 %.
84
Electrometallurgy and Ferroalloys Production
Molecular theory:
(CaO) + [FeS] = (CaS) + (FeO)
(CaO) + [S] + Fe = (CaS) + (FeO)
Ionic theory:
S + 2 e = (S2-)
(O2-) - 2 e = O
S + (O2-) = O + (S2-)
From the value of equilibrium constant KS we can create equation for [%S]
f o . %O . aS 2
%S
K S . aO 2 . f S
low activity of oxygen ao in steel (low content of dissolved oxygen and low vaoue
of activity coefficient fO)
low activity of sulfur anions aS 2 in slag
85
Electrometallurgy and Ferroalloys Production
C
Si
fS
O
% C, Si, O
1000
100
B3
L S=(S)/[S]
10
B2
1 B1
0.1
0.01 0.1 1 10 100
(FeO), %
160
140
120
100
LS
80
60
40
20
0
0 0.5 1 1.5 2 2.5
(FeO), %
86
Electrometallurgy and Ferroalloys Production
87
Electrometallurgy and Ferroalloys Production
Influence of placing the blowing block in the bottom of the pan and
volume flow of argon on homogenization times
4 C
B
3 A
H
2
C
1
B
A
0
0 1 2 3 4 5
QV
The basic solution lies in moving the alloying into a device of pan metallurgy
Basic timeline:
Basic timeline:
88
Electrometallurgy and Ferroalloys Production
89
Electrometallurgy and Ferroalloys Production
Questions
90
Electrometallurgy and Ferroalloys Production
THEMATIC BLOCK 8
During the oxidation of chrome-rich iron melt by gaseous oxygen, the carbon
oxidized into CO and chrome in the melt into Cr3O4 (or to Cr2O3) based on reactions:
Go1873; cal.mol-1
C + O = CO g 5343 9,47.T
3
/4 Cr + O = 1
/4 (Cr3O4) 58047 + 25,48.T
Both partial reactions (oxidation of carbon and chrome) are exothermic reaction.
They differ by thermal dependence of Gibbs energy change (free enthalpy). Change
in G of the C CO reaction with increasing temperature becomes more negative
(affinity increases); in Cr Cr3O4 reaction, the G becomes positive with
temperature (affinity decreases).
At certain temperature, the oxidation of Carbon into CO occurs primarily, Carbon may
also reduce into oxides Cr3O4 according to the reaction:
1
/4 (Cr3O4) + C = 3/4 Cr + COg +52704 34,90.T
. % Cr
3 3
4 4
f . pCO
KC ,Cr
Cr
f C . % C
91
Electrometallurgy and Ferroalloys Production
From the given equilibrium constant, the relation for carbon content in the melt can
be expressed:
f Cr4 . % Cr
3 3
4
. pCO
% C f C . KC ,Cr
From this relation we can perform a simplified analysis of the main thermodynamic
factors that influence the resulting carbon content in the melt at certain Cr content in
the melt.
1550C
1850C
C
Influence of
temperature
18 %
Cr
Ni=0%
Ni=5%
C Ni=10%
Influence of nickel
content
Cr
pCO = 1
C pCO < 1
Influence of pressure
Cr
93
Electrometallurgy and Ferroalloys Production
Causes:
high temperature during oxidation refinement acts negatively on
dephosphorization (reversible reduction)
formation of very viscous chrome slag - worsening of the process kinetics
negative effect of chrome on the activity of phosphorus (eCrP= -0,044)
Reduction of Cr2O3 (or Cr3O4) bound in the heavily meltable spinels of chrome slags
using silicon can be expressed in an equation:
Relation for the Cr2O3 content in slag can be expressed from equilibrium constant by
reaction:
1
a SiO
3
.a4Cr 2
%Cr2 O3 2 2
Cr O .a3Si . K
2 3
94
Electrometallurgy and Ferroalloys Production
The additive of the reducing agents leads to decrease in Cr2O3 content but also
increase of CrO. The reason is gradual reduction of certain amounts of Cr2O3 into
CrO. At the same time, a bond of CrO.SiO2 is formed, which is difficult to reduce:
40
30
20
(%Cr)
10
0
0 2 4
B
Effects of Ti:
In stainless steels without Ti, formation of Cr23C6 type carbides occurs on the edges
of the grains. Formation of these carbides is accompanied by decreasing amount of
chrome near the grain boundaries (by diffusion), which leads to lowered resistance of
these boundaries against intercrystalline corrosion. Addition of titanium leads to
formation of TiC titanium carbides, which remain equally dispersed in the matrix
during solidification and thus limit the formation of damaging chrome carbides.
(3)
Inclusion of titanium is performed at the end of the reduction timeline (26 % FeTi) or
into the pan during tapping (70 % FeTi, with regards to the thermal balance).
95
Electrometallurgy and Ferroalloys Production
Solution:
production of steel with significantly lower amounts of carbon and nitrogen
(AOD, VOD).
stabilization by Nb
modification of forming non-metal inclusions by adding calcium - calcium
modifies Al oxides into calcium-aluminum globular inclusions, where
heterogeneous nucleation of titanium carbonitrates occurs with more difficulty.
96
Electrometallurgy and Ferroalloys Production
Acid EAFs in foundries are further divided in the USA especially in smaller furnace
units of 7-8 t. There is no acid furnace in the Czech Republic.
Lining of acid furnace may be comprised of silica pre-forms. Often, instead of silica
lining, the furnace walls are stomped as a template by silica sand bound by water-
glass, or creep-resistant clay may be added into the stomping mixture. The furnace is
repaired by the same mixture.
The lids are lined by silica by the same method as in base furnaces. Lifetime of a
silica lid on acid furnaces is longer.
Linings based on silica react with elements with higher affinity to oxygen than silicon
(Al, Ti and at higher temperatures, carbon). In acid furnaces, after lowering the
activity of oxygen below the value which usually corresponds with the equilibrium
with silicon, oxygen may transfer from the lining into the steel. In acid furnaces,
lowered activity of oxygen cannot be achieved to the same value as in base
furnaces. This fact has influence on mechanical properties of the produced steel.
97
Electrometallurgy and Ferroalloys Production
98
Electrometallurgy and Ferroalloys Production
THEMATIC BLOCK 9
Behavior of hydrogen and nitrogen during the course of
melting in an EAF
99
Electrometallurgy and Ferroalloys Production
A more significant mechanism than transfer of hydrogen into the pool under the arcs
2
aOH
K H ,O
a O . p H O
2
2
aOH K H ,O aO pH
2
2O
2 (OH-) _ 2e = 2O + 2H
(Fe2+) + 2e = Fe
2 (OH-) + (Fe2+) = 2O + 2H + Fe
100
Electrometallurgy and Ferroalloys Production
N2 2 N
N K . pN 2
f N2
Process of nitrogen dissolution in iron melt will be more significant:
at higher pN2 values
at higher values of the equilibrium constant K (i.e. higher temperature - the
process of dissolving nitrogen is endothermic)
at lower fN, values
The intensity of nitrogen transfer into the pool will also be influences by the value of
nitrogen diffusion coefficient, thickness of the diffusion layer, constant area of the
phases and composition of the metal pool. Overall in comparison with hydrogen, the
transfer speed of nitrogen from the gaseous phase into the metal pool is 4-6 times
slower which is related to lower values of the nitrogen diffusion coefficient in melted
iron in comparison with hydrogen (DN=5,5.10-9 m2.s-1, DH = 3,5.10-7 m2.s-1).
It is necessary to consider that this fact also make removing nitrogen from the pool
more difficult during its vacuuming or decarbonization.
101
Electrometallurgy and Ferroalloys Production
Oxygen and sulfur are (same as nitrogen) superficially active elements and their
presence on the surface of the melt acts as a kinetic retardant during the dissolution
of nitrogen because their atoms contain reaction places necessary for the dissociated
nitrogen and thus they significantly lower the nitrogen dissolution in metal reaction
speed.
At low content of sulfur (< 10 ppm) and consequent intense mixing of steel, the
amount of nitrogen can decrease significantly during vacuuming (sulfur does not
block transfer of nitrogen through the interphase metal-gas).
102
Electrometallurgy and Ferroalloys Production
A carrier gas (helium) is blown into the pool via an auxiliary block, which captures
certain amount of nitrogen dissolved in the pool just by passing through the melt.
The blown helium with a certain amount of nitrogen is then collected by a special
lid and lead into an evaluation unit, where its thermal conductivity is tested and
the composition of the reference mixture N2-He is calculated, which is in the next
phase brought into the pool and also into the detector.
At the end of this phase the measurement of nitrogen amount in the final gas
is compared with the amount of nitrogen in the reference gas. If the difference is
small, it determines the amount of nitrogen and the entire process is finished. If
this is not so, it is necessary to perform an approximating calculation of reference
gas composition for a new blowing.
103
Electrometallurgy and Ferroalloys Production
Head of the HYDRIS probe (NITRIS) before the final installation into a
cardboard pipe
104
Electrometallurgy and Ferroalloys Production
105
Electrometallurgy and Ferroalloys Production
106
Electrometallurgy and Ferroalloys Production
creating the necessary thermal conditions in the pool for optimal course of
metallurgical processes and for achieving required tapping temperature.
controlling the energy mode during the melting (highest consumption of electricity)
- static model x dynamic model
The simplest (but also outdated) way is to control energy mode based on a pre-set
timetable. Another group of an elaborate methods of control is based on
consuming a predetermined amount of electrical energy. These methods do not
guarantee optimal control of the EAF modes.
107
Electrometallurgy and Ferroalloys Production
Questions
108
Electrometallurgy and Ferroalloys Production
THEMATIC BLOCK 10
109
Electrometallurgy and Ferroalloys Production
110
Electrometallurgy and Ferroalloys Production
Furnace transformer
Is constructed similarly to the AC furnaces. Its purpose is to lower the voltage of the
grid to the operational voltage of the arc furnace for the required current load.
Suppression coils
AC rectifier
Is formed by a block of tens or hundreds of cooled high-voltage diodes or thyristors,
which are wired is series and in parallel with regards to the layout of the voltage load,
which is 40-140 kA overall based on the size of the furnace.
The positive pole of the rectifier is connected to the floor electrode (floor anode), the
negative pole (cathode) of the rectifier is connected to the graphite electrode.
111
Electrometallurgy and Ferroalloys Production
112
Electrometallurgy and Ferroalloys Production
113
Electrometallurgy and Ferroalloys Production
114
Electrometallurgy and Ferroalloys Production
L
I
QUI
D-S
OL
I
DIN
TE
R
FA
CE
4
4m
m
1
6
0mm
115
Electrometallurgy and Ferroalloys Production
High number of steel pins (rods) - contact pins (e.g. 150 - 400 pins approx. 45 mm
in diameter), which are laid out in a cylinder which passes through the bottom of
the furnace.
The gaps between these pins are filled with creep resistant, usually magnesite
lining.
The lower part of the pins is connected in the contact panel which is then
connected to the anode side of the rectifier.
The outflow of heat from the floor electrode is ensured by forced flow of cooling air
between the lower ends of the uncovered steel rods. The upper part of the pins is
in contact with the steel pool.
116
Electrometallurgy and Ferroalloys Production
The wear of the pins is similar to the wear of creep resistant material. In
combination with the swaged magnesite, the lifetime of this type of floor electrode
is more than 800 meltings. During the changing of the anode, it is removed as a
whole by a hydraulic cylinder under the furnace and changed for a new anode.
Thin (1,7mm) steel plates that are laid out in ring formation on the bottom of the
furnace and are melted into a steel bus at their lower end which is placed on the
lower base connected to the wiring from the rectifier.
The area between the individual rings (7-10 cm) are filled by a monolitic electric
non-conductive magnesite matter
Advantages: high active area of the plates, perfect cooling by a material from the
lining, additional air or water cooling is not required as opposed to other types of
floor anodes.
Another advantage is the balanced division of the current on a huge area on the
bottom of the hearth which allows for calm and uniform transit of current through
the melt. The diagonal area of the plates is sufficiently large for the current.
117
Electrometallurgy and Ferroalloys Production
less divergence of the arc towards the walls of the furnace - approx. 15 to 30.
change in the shape of the arc - direct, angular, diffusion, etc.
higher stability - voltage within the arc does not pass null
118
Electrometallurgy and Ferroalloys Production
After igniting the arc, a free space (called a well) forms under the arc down to
almost the bottom of the furnace. As a result of the burning of the arc, a circular
space from the material melted away forms around the electrode.
Due to the central placement of the electrode and vertical direction of the arc,
a single coaxial space of heat distribution forms. There are no hot stains formed
on the walls, which are common in triple-electrode AC EAFs.
The period in which the arc is surrounded by unmeltable scrap is longer in DC
furnaces than in AC ones, which leads to heat loss through the walls and lid and to
lower wear. This creates conditions for melting with extremely long arc (with
U = 650 V, l up to 700 mm), which significantly speeds up melting of the scrap.
119
Electrometallurgy and Ferroalloys Production
The consumption of electrical energy can be lowered by using additional natural gas
burners. These burners should be installed tangentially so that the flame does not
interfere with the arc area and does not impede its burning.
120
Electrometallurgy and Ferroalloys Production
Mixing of the pool in a DC furnace is from the metallurgical point of view very
favorable for these reasons:
it increases the speed and effectiveness of metallurgical reactions on the slag-
metal interface
it improves the control over the tapping temperature
sampling during the melting is more representative
In large DC EAFs, it is necessary to ensure mixing by blowing inert gasses through
the bottom of the hearth or using electromagnetic mixers.
121
Electrometallurgy and Ferroalloys Production
122
Electrometallurgy and Ferroalloys Production
The consumption of electrical energy in DC furnaces is about 10-15 kWh/t lower than
in AC furnaces, which represents 5-10 % of energy savings (average values without
the use of burners are within 300-350 kWh/t, some sources say the consumption is
up to 460 kWh/t). The main causes of lower consumption are:
only one electrode
o lower electrical losses - shorter grid, mounts, etc.
o lower heat losses by radiation
o lower heat losses through the opening around the electrode
better transfer of heat during the pre-melting - the arc is surrounded for a longer
time by steel waste (batch)
transfer of energy from the electrodes at higher voltage, i.e. lower loss of R.I2 in a
short grid
better transfer of heat into the pool (penetration of the arc, mixing of the pool)
induction losses are lower compared to an AC furnace
Noise of DC furnace
In the course of melting the scrap, the noise from the DC furnace is almost
identical with the noise from AC furnaces and reaches - based on the furnace size
- values of up to 110dB.
With the increasing scope of pre-melting the liquid phase, noise of a DC furnace
decreases and after pre-melting, it produces noise that is approx. 10 dB lower than
AC furnaces (95 dB 85 dB).
123
Electrometallurgy and Ferroalloys Production
124
Electrometallurgy and Ferroalloys Production
125
Electrometallurgy and Ferroalloys Production
High-impedance AC EAFs
126
Electrometallurgy and Ferroalloys Production
Questions
127
Electrometallurgy and Ferroalloys Production
THEMATIC BLOCK 11
The main ideas which are used in these processes can be summarized into 3 main
principles:
1. Use of heat of the leaving furnace gasses for pre-heating of the metal
batch
2. Post combustion treatment of the forming CO within the furnace or in the
pre-heating chamber
3. Use of carbon and oxygen as sources of further energy for melting
Flue gasses from the workspace of the furnace are diverted into the pre-heating
chamber where the steel waste is placed. By passing of the hot flue gass through the
128
Electrometallurgy and Ferroalloys Production
layer of waste, about 35 % of the flue gas heat is utilized with the waste being heated
to 550-650 C.
129
Electrometallurgy and Ferroalloys Production
130
Electrometallurgy and Ferroalloys Production
The common principle of all modifications is the pre-heating shaft, which is placed
over the EAF and which allows setting the pre-heated batch into the workspace of
the furnace.
131
Electrometallurgy and Ferroalloys Production
four skewed electrodes entering from the side into the workspace of the furnace
integrated preheating shaft for the batch is placed under the melting furnace.
132
Electrometallurgy and Ferroalloys Production
Oxygen Carbon
Lance Lance
Scrap n Hot Metal
400-600C ~1300C
Slag Door
1570-1590C
Batch or the steel waste is continuously fed through the side entrance into the
furnace using a vibration conveyor (width=1.2m, depth=0.3m), running through the
heat-resistant material lined pre-heating tunnel 16m long which is heated by flue gas
from the EAF and using combined natural gas burners up to 700 C (usually only
550-600 C).
133
Electrometallurgy and Ferroalloys Production
Works with liquid residue (up to 15 %), speed of the batch fed into the furnace is
such that it is gradually melted by submerging; after achieving the nominal weight of
the melting, the influx of waste is stopped (in a 70 t furnace for approx. 10 minutes),
the tapping temperature is adjusted and tapping is performed. Wiring of EAF may be
AC or DC. The arc is very stable because the process of melting always works a
liquid pool.
Steel waste, raw iron, HBI or DRI is used as batch. 30-40% of liquid raw iron may
also be used through a special through in the furnace casing. Shredded waste,
reversible waste, light waste, etc. may be used for pre-heating.
1620 C
1580 C
Temperature diagram
t/min
Charge feeding rate
1,080 tr/tal
MW
Nm3 /h
0 2 Time (min) 38 47 50
134
Electrometallurgy and Ferroalloys Production
1. Main aims and course of the new processes in electric steel production
2. Pre-heating of steel waste, advantages and disadvantages
3. Fuchs Shaft Furnace, description, parameters
4. Verticon Process
5. COMELT VAI electric arc furnace
6. CONSTEEL process
7. ContiArc process of steel production
8. Twin-hearth EAF (Twin Shell EAF)
135
Electrometallurgy and Ferroalloys Production
THEMATIC BLOCK 12
CONARC process
Converter process One furnace is filled by liquid raw iron with a trough, then
oxygen is blown in through the upper nozzle. In the second stage of blowing, DRI or
steel waste is added which partially cools the pool and stops it from overheating. In
the course of converter part of the process, the amounts of C, Si, Mn and P are
lowered. Then the lid with the nozzle is moved to the second hearth (where the
tapping of steel is occurring), steel waste and DRI are added to the furnace and a lid
with electrodes is moved over the hearth.
EAF process during which the melting of DRI and steel waste occurs as well as
overheating the steel to the tapping temperature using the electric arc utilizing
oxygen-burning burners and combustion of CO. At the same time, the converter
process is occurring in the second furnace.
136
Electrometallurgy and Ferroalloys Production
137
Electrometallurgy and Ferroalloys Production
DANARC PROCESS
combustion of outgoing gasses
synchronized blowing of oxygen through the floor lances,
supersonic nozzles and blowing of carbide materials by side nozzles.
138
Electrometallurgy and Ferroalloys Production
Tuyeres life
Scrap substitute use
Maintenance program
BURNER POST-COMBUSTOR
139
Electrometallurgy and Ferroalloys Production
E
l
ect
r
ic
al
ene
rgy E
l
ect
r
ic
al
ene
rgy
43
0 K
wh/
t 33
0Kwh/
t
C
a
rb
on C
a
rb
o
n
1
3
5Kw
h
/t 2
1
0K
wh
/
t
O
t
he
ro
x
id
abl
eel
eme
n
t
s O
t
he
ro
x
id
ab
l
eel
eme
n
t
s
7
0
Kwh
/
t 7
0
Kwh
/
t
N
a
tu
r
al
gas N
a
tu
r
al
gas
4
5
Kwh
/
t 7
0
Kwh
/
t
T
OT
AL T
OT
AL
6
8
0K
wh
/
t 6
8
0K
wh
/
t
DANRC
CONVETIONAL
F
u
me
s F
u
m e
s
1
3
0K
wh
/
t 1
3
0 K
wh/
t
E
l
ect
r
ic
ala
nds
h
el
ll
oss
e
s E
l
ect
r
ic
ala
nd
s
he
l
ll
oss
e
s
3
0Kwh
/t 2
5Kwh
/t
W
at
erco
ol
i
ng W
at
er
co
oli
ng
8
0Kwh
/t 8
5Kw
h/
t
S
l
ag S
l
ag
5
5Kwh
/t 5
5Kw
h/
t
140
Electrometallurgy and Ferroalloys Production
141
Electrometallurgy and Ferroalloys Production
142
Electrometallurgy and Ferroalloys Production
Questions
143
Electrometallurgy and Ferroalloys Production
THEMATIC BLOCK 13
operating frequency grid frequency 50 Hz, medium IP - 600 to 10000 Hz, high
frequency (laboratory) IP - up to 500kHz
power 50 kVA to 5 MVA
weight of the batch 1 kg up to 10 t
Alternating current flowing through the inductor created alternating magnetic flow
(field), which induces alternating electro-motoric current of opposing polarity within
the batch. Induced current creates eddy currents in the batch which causes gradual
heating of the metallic material to the required temperature and melting. Materials
that conduct electricity can be heated by induction, however they do not have to be
ferromagnetic.
144
Electrometallurgy and Ferroalloys Production
Furnace inductor along with the batch represent a considerable inductivity (L), which
delay the phase of the current against the voltage, which lowers the effect of cos
and the real power declines. A capacitor battery (C1, C2, C3 ...C) must be wired in
paralel to the inductor, which compensates for the unproductive induction component
of the current.
The value of added capacity would be high enough for the circuit to achieve parallel
resonance, when the circuit behaves like an ohmic resistance.
145
Electrometallurgy and Ferroalloys Production
146
Electrometallurgy and Ferroalloys Production
147
Electrometallurgy and Ferroalloys Production
Due to the so called skin effect (compression of current on the surface of the
conductor), the highest portion of the heat is induced in the surface layer of the
heated and melted batch. The depth of induced current penetration into the batch
can be determined from the empirical relation
50,3 .
f.
where: depth of the penetration of induced current into the batch; cm
... batch resistivity ; .cm
f .... frequency of the current; Hz
... relative permeability of the batch; H.m-1 (for non-magnetic materials is
~ 1, for magnetic materials is >1)
Pel b . I 2 . n 2. . . f . D . K
where: n ... number of threads in the inductor
D ... median diameter of the batch:
before melting: median diameter of the pieces
after melting: median diameter of the pool (crucible)
D
K ... correction coefficient, K = f( )
768oC
768oC
149
Electrometallurgy and Ferroalloys Production
Pel
768o C
A steep decline of permeability values of the batch and therefore also the
decline of Pel is related to the loss of magnetic properties of steel at heating (750 C -
Curie point). Gradual increase of Pel is related to the permanent rise of and D
caused by filling the crucible with the melt. The (chemical) composition of the batch
also has influence on and and the character of its change with temperature.
150
Electrometallurgy and Ferroalloys Production
In their character, most melting technologies are close to reduction re-melting in EAF
(the occurrence of oxidation processes is limited).
Metallic batch is composed based on the character of the steel produced by waste,
either alloyed or non-alloyed, and ferroalloys. Steel waste is often in the form of the
crucible (e.g. in form of bars).
Slags which are formed during the melting fulfill the covering function and limit the
penetration of nitrogen, hydrogen and oxygen into the forming pool.
After the batch is heated, the de-oxidation and alloying elements are inserted for
composition correction, homogenizing the pool, to check the temperature and
tapping.
151
Electrometallurgy and Ferroalloys Production
152
Electrometallurgy and Ferroalloys Production
Based on the type, these furnaces have either hinged inductor and crucible or the
whole workspace.
The lining of the crucible is formed by MgO, ZrO2 or Al2O3. They are rammed,
formation of monolithic layer is achieved at first meltings.
The disadvantage of MgO crucibles is that at low pressures, MgO can be reduced by
carbon from the pool
MgO(S) + [C] Mg(g) + CO(g) (52)
Mg then evaporates from the pool. The use of Al2O3 leads to an unwanted rise in Al
levels in the pool due to reduction processes.
Long-term retention and good mixing of the pool within the conditions of deep
vacuum allows to perform these actions during the production of steel in VIFs
lowering the amount of oxygen using homogeneous carbon reaction,
effective degasification,
lowering the amount of unwanted accompanying elements (Cu, Pb, Sn) and
alloying without excessive burning of alloying elements.
153
Electrometallurgy and Ferroalloys Production
2/H/ H2(g)
2/N/ N2(g)
The transfer of hydrogen does not cause problems and the amount of hydrogen of
1 cm3/100 g can be achieved. In case of nitrogen, the process occurs much more
slowly. This is due to lower values of diffusion coefficients of nitrogen in steel and
more pronounced decrease of its activity coefficient by the components of melted
steel. The oxygen and sulfur in the solution are significant superficially active
elements, which prevent adsorption of nitrogen and thus slow down the process of its
transfer from the melt into the gaseous phase.
154
Electrometallurgy and Ferroalloys Production
In VIFs, special types of steel are made, such as creep resistant, transformer, etc.
In creep resistant steel, oxide net is formed during melting in regular conditions on
the grain edges - this decreases the plastic properties of steel.
In vacuum, the net is disrupted due to the vacuum and the temperature.
155
Electrometallurgy and Ferroalloys Production
156
Electrometallurgy and Ferroalloys Production
ESR Electrodes
Crystallizer
made mostly out of copper in double-shell design
the shape of crystallizer is most commonly circular, there are also cubic or slab
crystallizers, or crystallizers of special cross-sections including crystallizers for
production of hollow ingots.
construction-wise, the crystallizer is usually immovable.
in a different construction solution, only a short crystallizer is used, in which the
melted slag and upper section of the ingot is where solidification occurs. The
entire crystallizer is lifted based on the height of the ingot. Crystallizer can be
also immovable and in that case, the main board descends with the ingot.
The parameters of remelting (voltage, current, power, stability of slag, slag surface
height and the electrode-ingot diameter ratio) must be in line so that a constant
melting and growth of the ingot is achieved with the same grain structure throughout.
The depth of submersion of the end of electrodes is kept to the optimum by
automatic voltage or current control. A constant course of melting can be
approximately kept using a smooth measurement of the weight of the electrode or its
length and keeping the power in check.
The biggest ESR device is in SaarStahl GmbH in Voelklingen. It is able to create an
ingot 2.1 m in diameter, up to 5m in length and weighing 160 tons. The process is
done by multiple changes of the electrode. The Inteco company has an ESR with the
crystallizer 1000mm in diameter and creates ingots weighing 14 tons.
157
Electrometallurgy and Ferroalloys Production
For ESR of lower diameter (< 500mm) slag in solid form is used, for higher diameters
of ingots it is pre-melted away from the ESR and then put into the device from the
top. If slag is used in solid form, an exothermal mixture has to be placed below the
electrode at the outset of the process, which ensures formation of liquid slag upon its
ignition.
158
Electrometallurgy and Ferroalloys Production
During ESR, high level of desulfurization can be achieved - between 20-80 % in fact.
The level of desulfurization depends on:
the amount of sulfur in the material being remelted,
its overall composition,
composition of the slag,
composition of the atmosphere over the slag,
on the energy mode during remelting etc.
For ESR, the most frequently used slags are based on CaF2 (e.g. 70 % CaF2 30 %
Al2O3; 80 % CaF2 20 % CaO, 60 % CaF2 20 % CaO 20 % Al2O3). These slags
have relatively low dividing coefficient of sulfur LS = 4 30, with the rising content of
CaO the LS increases. A negative effect of SiO2 was proved on the achieved values
of LS.
High speed of desulfurization is not only a function of LS, but also of the kinetics of
the process. Highly liquid slag allows for more expanded course of diffusion
processes. Similarly, intense oxidation of sulfur may occur from the slag by the gas
phase into SO2.
during the melting of steel, conditions are created which are ideal for re-solution
of a significant portion of inclusions, which were formed by homogeneous
exothermal reactions during solidification of steel
during crystallization, a directed front of solidification is slowly formed and
thus conditions of rising of inclusions are created.
ESR is used for remelting of not only classical steels, but also highly alloyed steels,
superalloys and non-ferrous metals. Steels are utilized in electrical engineering
industry, aviation, in production of complex ball bearings, etc. i.e. where there are
increased requirements on homogeneity and micro-purity of steel.
160
Electrometallurgy and Ferroalloys Production
The basis of the ESRR process is in using crystallizer of so-called T-shape. Its lower,
narrower part corresponds to the required diameter of the resulting remelted ingot.
The upper part of the crystallizer is expanded and its diameter is defined based on
the maximum diameter of the ingots used for remelting. By remelting the ingots
(electrodes) of greater diameter into ingots of smaller diameters, the speed of their
production is increased. Usually, diameters 2-3 times larger than the diameter of the
resulting ingots are chosen (MPT International 5/96, p.48).
161
Electrometallurgy and Ferroalloys Production
162
Electrometallurgy and Ferroalloys Production
THEMATIC BLOCK 14
Ferroalloys production
Ferroalloys are alloys of iron and other metals and non-metals, e.g. FeMn, FeCr,
FeP.
Ferroalloys contain:
basic element - Fe, Si (basis)
main element - Mn, Cr, V (the main reason for its production)
unwanted inclusions - the content is not limited, ferroalloys also contain
various unwanted inclusions
harmful inclusions - their content is limited into a few 1/1000 %
Ferroalloys are used for alloying, deoxidation and for steel and alloy
modification, which is essential not only in steel production but also in production of
non-ferrous metals.
163
Electrometallurgy and Ferroalloys Production
Division of ferroalloys:
Carbo-thermal processes
The principle of carbo-thermal processes is the reduction of metal oxides by
carbon while creating stand-alone metals of these oxides (an analogy of BF
processes).
Reduction reaction is conditioned primarily by stability of oxides at high
temperatures. Stability of oxides is determined by the change in free enthalpy during
the formation of oxides from basic elements.
164
Electrometallurgy and Ferroalloys Production
The more negative the G is, the more stable the oxide is. The least stable
ones are MoO3 and WO3, the most stable ones are CaO, MgO, Al2O3 and this is why
they are the most difficult ones to reduce.
practical consequence:
at higher temperatures, some oxides can be reduced by carbon
by increasing the temperature, more stable oxides can be reduced
CO is gaseous, it leaks from the reaction area - pCO (advantageous)
lower oxide (such as TiO) is more stable than a higher oxide (TiO2).
Theoretically then, every element that forms a more stable oxide can become
reducing agent of a less stable oxide. For practical realization of this reaction, it is
necessary that the difference in G is great enough (n.104 J). If this difference is not
sufficient then the reduction does not occur completely and the resulting alloy
contains increased amounts of the reducing element.
Usually this element is comprised of more oxides. Lower oxides are more
stable then higher oxides. In some cases, lower oxide can be irreducible even if it is
reducible as a higher oxide.
165
Electrometallurgy and Ferroalloys Production
During reduction of oxides by carbon, not only pure metals are produced but
also corresponding carbides of these metals (thats why the produced ferroalloys
contain a certain amount of C). Carbides are formed because the G of their
formation is more negative than the G of sole metal production (in reduction of
166
Electrometallurgy and Ferroalloys Production
an metal oxide by carbon). The greater this difference is, the more difficult the
production of a ferroalloy with low amount of carbon -the carbide is produced
primarily, which predetermines the higher amount of carbon in the ferroalloy.
Cr2O3 + C = Cr + CO G = -126 000 J.mol-1
Cr2O3 + C = Cr7C3 + CO G = -180 000 J.mol-1
A low amount of carbon in the produced ferroalloy can be achieved only is the
reaction occurs at high content of silicon in the ferroalloy. The change in free
enthalpy of metal silicide formation (MexSiy in general) is usually more negative than
the change of free enthalpy of carbide formation. Silicon displaces carbon from the
carbide bond (MeC) and silicides (MeSi) are formed, the surplus carbon is expelled
from the metal in form of graphite (analogous to the raw iron - outflow of graphite,
high content of Si in raw iron).
Reduction by carbon
(MexOy) + y C(s) x [Me] + y CO(g) metal H= +
(MexOy) + (y+z) C(s) [MexCz] + y CO(g) carbide H= +
Reactions are endothermal and form gaseous product (CO), therefore they are
accelerated by
increased temperature (higher outflow of the reduced element, higher use of
furnace lining, higher consumption of energy)
decreased pressure
168
Electrometallurgy and Ferroalloys Production
Metalo-thermic processes
The principle of metalo-thermic processes is the reduction of oxides using
metals with high oxygen affinity (such as Al, Si, Si alloys and others). This reduction
releases high amounts of heat:
without external influx of energy, very high temperatures are achieved
products of the reduction (with high melting temperature) are formed in liquid
state, thus the reduced metal is separated in form of drops. The reducing agent
(metal) oxidizes into a corresponding oxide and almost fully moves into the slag.
The most common element for reduction is Al or Si - we then designate these
processes aluminothermy or silicothermy. Reduction of MeO using Al is
characterized by a more negative H (the reaction is highly exothermic) than the Si
reduction. Therefore, heating is essential during reduction by Si. (another reason for
heating: formation of silicides - higher temperature is necessary for their dissolution).
Aluminothermy has the advantage of lower C content in the resulting ferroalloy
(C is between 0,05-0,1 %). Products include: low-carbon FeW, FeMo, FeCr, FeMn,
FeV, FeTi, FeNb, FeTa and ferroalloys TiAl, CrAl.
The initial material for aluminothermy requires refinement in terms of
damaging inclusions (especially S, As, Sn, Pb, P < 0,05-0,1 %), because the slag
that forms has relatively low refining effect.
Thermodynamic aspects
For simplification, the reaction is presented by the example of TiO2 reduction using
Al.
169
Electrometallurgy and Ferroalloys Production
The residual amount of TiO2 in the slag (a criterion of yield from the reaction in case
of balance) is determined by this relation:
Thermal balance
Thermal dynamics and the absolute value of H are determining factors of
thermal balance of a metalothermic reaction. It is also necessary to consider:
H of the formation of silicides or aluminates in metal
H of formation of silicates or aluminates in the slag
Q necessary for heating and melting of the initial substances and the products
in T of the reaction
170
Electrometallurgy and Ferroalloys Production
Q of thermal loss
H of the accompanying exoreactions, Q in heating (eventually), pre-heating of
the batch
For example the reaction
(Fe2O3) + 2[Al] (Al2O3) + 2[Fe] H0298 = 854 kJ/mol
- is strongly exothermic and ensures formation of products (Fe and Al2O3) in
liquid state.
However in the reaction:
3(MnO) + 2[Al] (Al2O3) + 3[Mn] H0298 = kJ/mol
- sufficient temperature is not present for melting of the aluminate slag. If we
exchange MnO for Mn3O4, the H0298 = - 2535kJ/mol and the thermal effect will be
sufficient.
Conclusion:
Enthalpy of the acquired slag, metal and thermal loss are approximately the same
for the individual metals (assumption).
A rule has been established:
Aluminothermic process after ignition occurs spontaneously if the amount of
developing heat corresponding to 1 g of the batch (this includes slag-forming
additives) is greater than appox. 2300-2700 J.
Sometimes this value is compared (not entirely correctly) to the specific
thermal effect of an aluminthermic reaction
H 0298
q cal/g of the batch (MeO+Al)
n MeO M MeO n Al M Al
The value of q does not consider the mass of the slag-forming additives and is
valid for 298 K. However it is a suitable rule for judging (and comparing) the course.
The values of q are tabulated.
The following is evident from these values:
most metals for alloying steel can be aquired by Al reduction from their higher
oxides
when using Si, reduction is only possible for Mn, Mo, Cr (others only with
provision of external heat)
Under spontaneity, we consider not only the condition of negative G, but also
sharp division of metal and slag
optimal amount of Al and Si additives, so that liquid slag is obtained: MeO-Al2O3,
MeO-SiO2 or MeO-SiO2-Al2O3
amount of additives should not be lower than 200 kg (so that the heat loss is not
too great)
171
Electrometallurgy and Ferroalloys Production
Another way for increasing yield (and often also the option for performing
aluminothermic reduction in terms of thermal balance) is utilizing collateral
exothermic reactions. For this purpose, MeO oxides with low H0 (of MeO formation)
are suitable. In other words - with low affinity to oxygen such as FeO, Fe3O4, Fe2O3.
Iron reduced from FeO or from Fe2O3, Fe3O4 acts favorably in the forming alloy on
the yield with its diluting effect.
Options of the collateral exo reactions:
use of higher Me oxide instead of or with the MnO (e.g. MnO2+MnO, CrO3+Cr2O3
etc.)
use of Me salts that contain oxygen (e.g. KMnO4); use of potassiom salts (KClO3)
use of higher oxide, which reduces only to a lower one and does not enter the
metal alloy, in form of a metal (e.g. CaO2 CaO+..., BaO2 BaO+ ...)
The course of collateral reaction requires increase in consumption of Al or Si.
The overall amount of slag is also increased.
Additional heat in reactions with insufficient H, can be acquired also by
preheating the components before igniting the mixture.
The melting temperature of Al2O3 slag from aluminothermic reduction can be
lowered by increasing the content of MeO, FeO, ZrO2, TiO2.
chunks slow the process, slag and metal must be liquid for a longer period so that the
reaction can finish. In first moments of the reduction, Me is depleded around Al and
an Al-Me drops form, which moves downwards through the slag layer and is further
refined from Al.
Reaction temperatures - 2200-2400 oC
In FeW production - 2500 oC
Re-melting processes
Aim:
To achieve a complex alloy
Multi-component alloys - remelting in an IF or VIF or EAF from pure components or
alloys.
173
Electrometallurgy and Ferroalloys Production
= 0
174
Electrometallurgy and Ferroalloys Production
R
2
1
Z R L
2
L C
If XL = XC then Z=R which are conditions for creation of serial resonance of the circuit.
In serial resonance, the circuit acts as if only a resistor was connected, i.e. the
current is in phase with voltage. Resonance may occur at constant frequency if we
change L and C or at constant L, C if we change the frez frequency. This frequency is
then called resonance frequency
1
f rez
2 L.C
C L 1
Z
1
C
L
175
Electrometallurgy and Ferroalloys Production
where is the phase shift between voltage and current teor. <-90; 90> and cos is
the power factor.
Three-phase current
12
0O
L1
L2
Star connection
Delta connection
L1
Preal = 3.Uptp .Iptp .cos
Preal = 3. 3 .Up .Ip .cos