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Modern Steelmaking Processes

2. Basic Oxygen Process – Steelmaking Practices

Topics to discuss…
1. Pre-treatment of hot metal
2. Sequence of operation in LD process
3. Process reaction and energy balance
4. Development in LD process

1
 Pre-treatment of Hot Metal
 Adjustment of the composition and
temperature of blast furnace produced
hot metal for optimal operation of BOP
• in the extreme case, the converter operation
is reduced to scrap melting and carbon
reduction only after the prior removal of Si, P
and S in the pretreatment steps
 Hence, pre-treatment of hot metal to remove Si, S and P prior to BOF
steelmaking has gained worldwide acceptance as an intermediate operation.
 Developed primarily in Japan, pre-treatment
involves two or three processing steps:
• The first step is desiliconisation
using mill scale, sinter fines, Mn ore, Iron ore
(to residual Si < 0.15 %)
• After deslagging, the hot metal is desulphurised
and dephosphorised by injecting with nitrogen
plus oxygen and mixture of sinter fines, burnt lime,
calcium fluoride and some calcium chloride.
• In some practices, sodium carbonate alone is
injected.
• Important benefit of pre-treating P and S
ability to produce steels with P and S contents
lower than otherwise achievable without severe
penalty to the converter process
• Important benefit of pre-treating Si
reduce chemical attack on basic refractory lining
and use of only minimal amounts of slag-making
fluxes, thereby maximizing process yield.
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 despite its obvious advantages
(improved dephosphorisation, reduction in
slag volume, lower consumption ferro
alloys during BOF steel making),
desiliconisation pre-treatment is
not practiced due to the problems
in handling highly siliceous slag
(extremely fluid, causes aggressive attack
on most refractories)
 Instead, efforts have been made
to produce low silicon (0.3-0.6 %)
hot metal directly in blast furnace.
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Changes in refining functions in the Japanese steel industry
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Hot metal refining with Na2CO3 in torpedo car

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Hot metal refining with lime-scale-salt in torpedo car

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Hot metal refining with lime-scale-salt in transfer ladle

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Reagents for hot metal pre-treatment
• Soda ash
 effective for both desulphurization and desiliconization
Location of hot metal
 disposal of soda bearing slag is problematic pre-treatment
 also generates dense fumes on addition to hot metal • blast furnace runner
• Calcium carbide and Magnesium granules • transfer ladle
 highly efficient desulphurizing agents • torpedo
 calcium carbide along with lime is injected into the bath
 magnesium granules help reducing injection time and slag volume

• Mill scale, sinter fines, Mn ore, Iron ore

 used to desiliconize hot metal

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Sequence in Operation in LD Process

1. Scrap charging (in inclined position)
[3-5 min]
2. Vessel rocking to drop scrap at the
bottom and hot metal charging (in
horizontal position) [3-5 min]
3. Rotating to vertical position, lowering
the lance and first blowing of oxygen
starts [1-1.5 min]
4. As soon as ignition starts, flux is
charged to form early slag; blowing
continues [15-25 min]
5. Blowing is stopped, lance is raised, vessel inclined
position for bath analysis and temperature
measurement; alloy additions made; 2-3 min waits
for homogenisatiton [5-8 min]
6. If analysis and temperature is correct, vessel is
rocked in tapping position and tapping in ladle;
deoxidation and alloy addition in ladle [4-7 min]
7. As slag appears, vessel is inclined further to tip
out the slag [variable]
• Efficient tap-to-tap time 30 – 33 minutes
• Good tap-to-tap time 40 – 45 minutes

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 Schematic of operational steps in
oxygen steelmaking process (BOF)

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1st stage:
blow time – 5-6 min
Blowing rate 10,000 Nm3/hr oxygen pressure – 11 atm
lance height – 130 cm

2nd stage:
DESLAGGING

blow time – 15-18 min

oxygen pressure – 8-9 atm
lance height – 110 cm
after all lime addition,
oxygen pressure – 11 atm
lance height – 90 cm

typical blowing practice in LD process

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 • Initially oxygen is blown soft by keeping lance
distance higher to promote slag formation and
to avoid ejection of small particles, because
hot metal is not covered by slag.

• Oxygen is blown for nearly 15-20 minutes by

progressively decreasing the lance distance
such that slag foaming remains under control
and oxidation reactions occur uninterruptedly.

Physical state of the BOF

in the middle of the blow

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Process Reaction and Energy Balance

Silicon Reaction
• The strong affinity of oxygen for Si results
removal of almost all Si early in the blow.
• Si dissolved in hot metal (0.25–1.3 wt.%) is
oxidized to very low levels (<0.005 wt.%) in the
first 3 -5 minutes of the blow.
• The silicate slag reacts with the added lime
(CaO) and dolomitic lime (MgO) to form the
basic steelmaking slag.
• The exothermic reaction produce significant
heat, raises the bath temperature and strongly
affects the amount of scrap that can be melted.
• It also determines the slag volume and
consequently affects the iron yield and
Variation of composition of metal during the blow dephosphorization of the metal. In general,
more slag causes less yield but lower P.

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 Manganese Reaction
• Like Si, Mn is oxidized to MnO early in the
blow up to a certain level and it remains
there for almost the rest of the blow.
• However, at the end of the second period,
and after most of the silicon has been
oxidized, the Mn reverts into the metal.
• Towards the end of the blow the Mn in the
metal decreases again as more oxygen is
available for its oxidation.

Variation of composition of metal during the blow

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Carbon Reaction
• C in the hot metal is oxidized to CO and CO2
during the oxygen blow, and steel with less than
0.1 wt% carbon is produced.
• The change in the carbon content shows three
distinct periods.
 The first period occurs during the first few
minutes of the blow, shows a slow
decarburization rate as nearly all the oxygen
supplied reacts with the silicon in the metal.
In fact, the curve shows a slight increase as
percentage of Si and Mn decreases in the
bath.
 The second period, occurring at high carbon
contents in the metal, shows a constant
higher rate of decarburization and it is
Variation of composition of metal during the blow controlled by the rate of supplied oxygen.
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  Finally, at the third period, the decarburization
rate drops as carbon becomes less available to
react with all the oxygen supplied.
At this stage, the rate is controlled by mass
transfer of carbon, and the oxygen will mostly
react with iron to form iron oxide.
Also in this stage, the generation of CO drops
and the flame over the mouth of the furnace
becomes less luminous, and practically
disappears below about 0.1 wt.% carbon.

Variation of composition of metal during the blow

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Phosphorous Reaction
• Dephosphorization is favored by the oxidizing
conditions in the furnace.
• As P removal is favored by low temperatures,
high slag basicity (high CaO/SiO2 ratio), high
slag FeO, and high slag fluidity, P content
decreases very slightly up to the end of the
second period of the blow.
• During this period, FeO increases, stirring due
to CO formation improves slag-metal mixing,
CaO addition and its dissolution raises slag
basicity, and fluorspar added to raise fluidity of
the bath.
• Thus, P removal rate accelerates till the end of
the blow when temperature is high and the bath
is deoxidised.
Variation of composition of metal during the blow
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 Sulphur Reaction
• The BOF is not very effective for sulfur removal
due to its highly oxidizing conditions.
• Sulfur distribution ratios (S)/[S] in the BOF is
about 4–8, which are much lower than the
ratios in the steel (~300–500) during secondary
ladle practices.
• In the BOF, about 10 to 20% of sulfur in the
metal reacts directly with oxygen to form
gaseous SO2.

Variation of composition of metal during the blow

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Slag formation
• Fluxes are charged into the furnace early in the blow and they dissolve
with the developing oxides to form a liquid slag.

• The rate of dissolution of these fluxes strongly affects

the slag-metal reactions occurring during the blow.

• At the beginning of the blow, the tip of the oxygen

lance is kept high above the bath surface, at
about 3.5 m (12 ft), which results in the formation
of an initial slag rich in SiO2 and FeO.
• During this period large amounts of burnt lime and
dolomitic lime are charged into the furnace.

change in slag composition

with blowing time

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• The lance is then lowered and the slag starts
to foam at around one third of the blow due
to the reduction of the FeO in the slag in
conjunction with CO formation.
• Also, as the blow progresses, the CaO
dissolves in the slag, and the active slag
weight increases.
• Finally, after three quarters into the blow, the
FeO content in the slag increases because
of a decrease in the rate of decarburization.
change in slag composition
with blowing time

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• During the blow, the temperature of the metal gradually increases from
about 1350°C to 1650°C at turndown, and the slag temperature is
about 50°C higher than that of the metal.

• The slag at turndown may contain regions of undissolved lime mixed

with the liquid slag, since the dissolution of lime is limited by the
presence of dicalcium silicate (2CaO•SiO2) coating, which is solid at
steelmaking temperatures and prevents rapid dissolution.

• The presence of MgO in the lime weakens the coating. Thus, charging
MgO early speeds up slag forming due to quicker solution of lime.

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 The resulting slag at turndown in top-blown • The quantity of slag, which is zero at the
converters (BOF or BOP) have typical ranges: beginning, keeps increasing during the
blow as lime dissolution continues
42–55 % CaO 3–8 % MnO
2–8 % MgO 10–25 % SiO2 • Total lime used depends primarily on the
SiO2 content so that CaO/SiO2 = 3 is
10–30 % FeOT 1–5 % P2O5 maintained in the final slag to ensure
1–2 % Al2O3 0.1–0.3 % S adequate refining
• Extent of lime added varies between
 In the OBM (Q-BOP) or bottom-blown converter, 60-70 kg/ton liquid steel for 0.5-0.7 % Si
the total FeO in the turndown slag is lower, ranging to up to 120 kg/ton for 1.2 % Si.
between 4–22 %.

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Heat Balance of Basic Bessemer Process

Heat Input Item Per Cent Heat Output Item Per Cent
Heat of molten pig iron 42 – 44 Heat of steel 52 – 54
Carbon oxidation 18 – 20 Heat of slag 18 – 20
Oxidation of Si and Mn 7–9 Heat of waste gas 22 – 24
Iron oxidation 2–3 Blast moisture dissociation 1 – 1.4
Slag formation 7–9 Heat losses 3–4
100 100

• Total heat input (and output) is roughly equal to 2500 MJ in BOP

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 Developments in LD Process
 LD process was originally designed to [1] refine basic pig iron < 0.4% P),
[2] to consume ~25% scrap as coolant ,and [3] to produce soft steel (low C)

 Being established as the major steelmaking process, the process undergoes

several modifications:
• increase in vessel size
• modification in vessel shape (design of mouth, change in height to diameter ratio)
• introduction of multi-hole nozzle (3-7) lance instead of single-hole lance
• use of high-quality refractories to improve lining life from 100s to 1000s heats.
• the process goes to nearly full automation
• design process to deal Thomas iron (high P grade pig iron)
• improvement in thermal input to use more scrap
• more efficient use of CO-rich flue gas for energy recovery

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LDAC or OLP Process

LDAC – Linz, Donawitz, ARBED-Dulange, CNRM; OLP – Oxygen Lance Powder

• Principal aim to use Thomas grade pig iron containing more than 0.4% P
• Dephosphorisation is improved by introducing powdered lime through the lance
along with oxygen

oxygen
lime lime

oxygen lance designs to introduce lime powder along with oxygen

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• The charge contains less scrap to accommodate more lime
needed to remove extra P.
• At least one intermediate phosphoric slag is removed from
the vessel and further lime is added and oxygen blown to
finish the heat

• P level is reduced below 0.02%.

• If extra-low P needed, the process use two intermediate slags:
 1st – fertilizer grade
 2nd – throw away
 3rd – retained for next heat

• Steels containing C as high as 0.8% can be produced characteristics of the OLP process

• Little lower production rate and higher refractories consumption

than the LD process
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LDAC Process LD Process

Pig iron C = 3.2 - 3.5% Pig iron C = 4.0 - 4.5%
P = 1.5 - 2.0 P = 0.5 - 0.45
Mn = 0.7 - 1.0 Mn = 0.4 - 2.5
Si = 0.4 - 0.6 Si = 0.65 - 1.4
S = ~ 0.05 S = 0.02 - 0.06

Slag Intermediate Final Slag CaO 47 – 52

CaO 45 - 50 ~50 MgO 2-5
P2O5 18 - 20 ~10 P2O5 1-3
SiO2 5-8 2-4 SiO2 10 – 16
Fe 10 - 11 20 - 24 MnO 3-5
Fe 10-11

• Vessel volume is 20% more than that of LD vessel

(capacity 1.0 m3/ton, compared to 0.75 m3/ton for LD vessel)
• Tap-to-tap time is 55 - 60 min
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 Kaldo Process

• Similar to LD process
 refine molten iron by gaseous oxygen
 similar vessel, shape, lining, lance, etc.

• Unlike LD process, the vessel is rotated (~30 rev/min) along its long axis during refining

Purpose of rotation
• Most CO is burned to CO2 inside the vessel, so rotating is essential to safeguard the lining
• some heat is transferred from gas to liquid metal through heated lining
• better mixing of slag, gas and metal to hasten refining

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Advantages Disadvantages (compared to LD type)

• easy process control and pig iron of any • tap-to-tap time (44-60 min) is almost twice
composition can be used as long as in the LD process

• ability to use a high proportion of scrap metal • higher capital cost

(up to 40-50%)
• good controllability of final steel specification;
steel with extremely low level of impurities can
be made
• more difficult to upscale to higher outputs
• additional complexity (i.e. rotating parts
and loading thereof)

• high yield due to low loss of Fe in slag and gas • low lining life (50-100 heats, i.e., almost
1/10 of that of LD process)

In view of these drawback (especially the last one),

the Kaldo process has found only a limited application.
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 lime and
waste charging ore feed
gases movable
gas duct position
addition
pipe

cooling water

tapping diagram of a melt by the Kaldo process

position a - skimming of 1st slag; b - skimming of 2nd slag;
tapping c - tapping of steel (0.018% P, 0.013% S, 0.002% N);
ladle

Slag 1st 2nd Final

CaO >50 >50 40 - 50
P2O5 >18 10 - 12 6-7
operation in a Kaldo vessel SiO2 ~8 ~6 4
Fe 10 - 12 18 - 20 25 - 30

Rotor Process
holes for
holes for
charging and
removal
oxygen blow
of gases
primary oxygen
(high purity) lance
metal level
tuyere for secondary
oxygen (70-75% pure)
rotor
rotation

rotor slope • Oxygen supplied through 2 lances:

A rotor furnace
• A long cylindrical vessel (called rotor)
of L/D  4 is used
• 360° rotatable along horizontal axis;
can also be tilted to 90° in the vertical
plane; rotating speed 0.2 – 4 rpm
 the principal one supply oxygen for refining is immersed into
the bath
 the second one supply oxygen for burning of CO gas to CO2
and utilise the heat for steelmaking
 By cutting off the second lance and immersing the primary one,
the furnace atmosphere containing CO only can be made
 If oxygen supply is cut off completely, FeO content in slag will
diminish due to FeO+CO reaction
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 Difficulties in Rotor process

• long tap-to-tap time (80-90 min)

• lower productivity
• higher cost and complexity in
operation
• low lining life

Variations of metal composition variation of oxygen content of

during blowing slag with the composition of
furnace atmosphere

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