2.1.

3 DESULFURIZIATION IN SECONDARY STEELMAKING

Except in free-cutting steels, sulfur is considered to be a harmful impurity,
since it causes hot shortness in steels. Some decades back, for common grades
of steel cast through the ingot route, the maximum permissible sulfur content
was 0.04%. In the continuous casting route, it should be 0.02%. In special steel
plates, the normal specication for sulfur is 0.005% these days, but there is a
demand for ultra-low-sulfur (ULS) steel with as low as 10 ppm (0.001%), e.g.,
in line pipe, HIC resistive steels, and alloyed steel forgings.
Sulfur comes into iron principally through coke ash. It is effectively removed
from molten iron by slag in a reducing environment only. Hence, traditionally,
sulfur control used to be done during ironmaking in a blast furnace. Very little
sulfur removal is possible in primary steelmaking due to the oxidizing
environment. An exception is the electric arc furnace (EAF), where low-sulfur
steels are produced through two-stage rening.
In view of the consistent demand for lower-sulfur steel and the incapability of
the blast furnace to achieve it, external desulfurization of liquid iron in a ladle
during transfer to the steelmaking shop was developed. The process is capable
of lowering sulfur content to 0.01% or so and is an essential feature of a modern
integrated steel plant.
Content below 0.01% must be accomplished in secondary steelmaking.
There are now pro-cesses, such as the MPE process of Mannesman and the
EXOSLAG process of U.S. Steel, where desulfurization is achieved to some
extent during tapping by using synthetic slag and utilizing the kinetic energy of
the tapping stream. Desulfurization by treatment with synthetic slag on top of
molten steel and gas stirring (either in an ordinary ladle, in a ladle furnace or
VAD, or during vacuum degassing) are also being practiced.
However, only the injection of a powder such as calcium silicide into the melt
is capable of producing ULS steel. ULS can be achieved only if the dissolved

oxygen is also very low. Gas stirring is required, so deep desulfurization is

associated with deep deoxidation. The use of alumi-num in combination with
calcium or rare earth (RE) metals achieves both. In addition, injection processes
are capable of inclusion modication for further improvement of the properties of
steel. A low nitrogen level has been achieved in low-sulfur and low-oxygen
steels. This is an additional benet if deep desulfurization is done before or
during vacuum treatment. Furnace slags contain oxides such as FeO, SiO2,
P2O5, and MnO. These oxides are unstable in the presence of a deoxidized steel,
especially when the slag and steel are intimately mixed. As a result, some
reversion of phosphorus into the steel occurs. This slag also partly consumes
added deoxidizers, so it does not allow proper utilization of them for steel
deoxidation. The slag also causes wear on the ladle lining. (Although these have
been known for a long time, very little physicochemical investigation has been
conducted on these effects. Turkdogan has considered some aspects of the
reaction of liquid steel with slag during furnace tapping. It is best if slags from
primary steelmaking furnaces are not allowed into the secondary steelmaking
ladle. However, this is difcult to implement. In addition, some slag is required
for desulfurization during secondary steelmaking and other benecial effects.
Therefore, control of furnace carryover slag aims at the twin strategy, viz., (a)
minimization of furnace carryover slag, and (b) modication of carryover slag by
the addition of uxes (principally CaO, but also Al, SiO2, Al2O3, and CaF2 to
some extent) to render desirable properties to it.

2.2.3

THERMODYNAMIC OF DESULFURIZIATION IN SECONDARY

STEELMAKING

A.

SOLUTION OF SULFUR IN LIQUID STEEL

At steelmaking temperatures, sulfur is a stable gas, with the most predominant

molecule being S2. The dissolution of sulfur in molten steel may be represented
by the following equation:
1/2 S2 (g) = S

(1)

For the above reaction,

h S

K 1= --------pS2

(2)

where K1 is the equilibrium 2 constant for Reaction (1), p S denotes partial

pressure of sulfur in the gas phase in atmosphere, and hS is the activity of
dissolved sulfur in steel with reference to 1 wt.% standard state.
Again,
6535

log K1 = ----------- 0.964

T

(3)

The interaction coefcients describing

the inuence of some common
j
solutes (j) in liquid steel on the activity coefcient of sulfur (fS) dissolved in
liquid steel (i.e., e s ) at 1600C. where hS = fS WS, WS being the weight
percent of sulfur in steel. It may be noted further that the solubility of sulfur in
molten steel is very high.

B.

REACTION EQUILIBRIA OF SULFUR

Ca and Ba form CaS and BaS, respectively, upon reaction with sulfur, whereas
cerium forms several suldes7 out of which CeS is the stablest one under
steelmaking conditions. Ce also forms an oxysulde, Ce2O2S. All of these
compounds are solids at steelmaking temperatures. It may be noted, from
thermodynamic data on these compounds in any standard text, that all these
elements form very stable suldes as well as oxides. Therefore, they are both
strong deoxidizers as well as desulfurizers and would form both oxides and
suldes.
Again, these compounds would not necessarily be present in a pure form. For
example, addition of Ca-Si leads to the formation of a CaO-SiO2-type
deoxidation product . However, we do not propose to get involved in these
complexities and consider the overall reaction to be

S + (MO) = O + (MS)

(4)

For the limiting case of unit activities of MO and MS (i.e., assuming pure MO
and pure MS), the equilibrium constant (KMS) for Reaction (4) is
hO

W O

hs

Ws

K MS = ---------- = ------------- (at equilibrium)

(5)

The values of KMS for different systems can be calculated from the free energy
of reaction. Figure 1, reproduced from Turkdogan, shows the pattern. Ba is the
strongest desulfurizer and Mg the weakest, with Ca and Ce lying in between.
Holappa has reviewed the theoretical basis for sulfur removal in ladle
treatment by slagmetal reaction. If the MO and MS are not pure, then it is
better to utilize the general ionic form of desulfurization reaction, viz.,
[S] + (O2) = (S2) + [O]
(aS2- ) [ho]
K= --------------------------[hs] [WO2- ]

(6)
(7)

FIGURE 1 Oxygen/sulfur activity ratio in liquid iron for some sulde-oxide

equilibria at 1873 K.
(aS2- ) [ho]
(K 6 )(a o2- )= ----------------------[hs]

(7)

If we replace a 2 with weight percent sulfur in slag (i.e., WS), then we may use
a modied value of K6 (let it be K 6 ). Then,

K 6 (a

W S h O

) = -------------------------- = C S

(8)

hs

where C S is known as the modied sulde capacity.

the sulde capacity of slag (CS), i.e., the ability of a slag to absorb sulfur, was
originally dened by Richardson as

C S = (W S )( p O2 / p S2 ) 1/2

(9)

where (WS) is the weight percent sulfur in the slag in equilibrium with a gas
2

having partial pressures of oxygen and sulfur as p O

and pS . Its usefulness

stems from the fact that CS is a property of slag, and at a xed temperature it is
determined solely by slag composition. The higher the value of CS, the better the
desulfurizing ability of the slag. Figure 2 shows CS values for some typical slag
systems of interest in secondary steelmaking.9 The superiority of CaO-CaF2
slag is obvious. Values of CS for various slags are available in Slag Atlas.10
CS is determined by equilibrating the slag with a gas mixture having known
oxygen and sulfur potential. However, it is the slagmetal equilibrium that is of
interest. This requires the use of a modied CS (viz., C S ) as dened in Eq. (8).
The relationship between CS and C S is

936

log CS = log C S + -------- 1.375

T

(10)

At 1600C, C S = 5 CS.

FIGURE 2 Sulde capacities of some slags at 1873 K.9

(Another parameter of interest is the equilibrium sulfur partition ratio between
slag and metal (LS), where LS = (WS)/[WS]. From Eq. (8), if [hS] is taken as
[WS], then, at slagmetal sulfur equilibrium,
Ws

L S = ---------- = ---------[Ws]
[ho]

(11)

hO in liquid steel is typically determined by the presence of a deoxidizer,

especially dissolved aluminum. One may relate hO to the FeO content of slag as
well. However, it has been found more appropriate to relate it to the former.
Figure 3 shows LS as a function of the CaO content of slag and aluminum
content of metal for CaO-Al2O3 slag. Therefore, for good desulfurization, Al
content of more than 0.020% is generally recommended.