06

Sulphur Problem

Today’s Topics

• Introduction
• Behaviour of sulphur in metal and slag
• Oxidation of sulphur in the furnace
• Oxidation of sulphur in the ladle
• Conditions for desulphurization
 Introduction

 It is generally considered that sulphur is of  Source of sulphur in steel

no value in steel.
• pig iron
• steel scrap,
 Sulphur contributes
especially in oily steel chips
• red-shortness and susceptibility to overheating
• fuel (high-sulphur fuel oil, gas
in wrought steels
produced from high-sulphur coals)
• ingot cracking and low ductility in cast steels.

 In many steel specifications, for that reason,

the maximum permissible S content is
limited between 0.03 - 0.06 wt% S.

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Behaviour of Sulphur in Metal and Slag

 S has unlimited solubility in liquid iron, but limited solubility in solid iron.

 sulphur contents only about 0.001-0.1 wt% are typical in steelmaking.

 Sulphur dissolves in iron from its gaseous state with evolution of heat:
1/2{S2} = [S]1wt% ; DG° = -72,000 - 10.25 T J/mol

 a high DH° indicates that certain bonds existing between S and Fe in the solution
 S does not pass into the gaseous phase in elemental [S] form

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  The solutions of sulphur in pure iron exhibit appreciable negative
deviations from Henry's law.
• activity of sulphur in molten steel depends on the composition of steel

The activity coefficient of S increases

with increase in C, Si and P

Influence of sulphur content, and of third elements added to iron-

sulphur solutions, on the activity coefficient of sulphur at 1600°C
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 Sulphides are completely soluble with silicate slags at high temperatures,

and show extensive solubility at iron- and steelmaking temperatures

 Solubilities of CaS in CaO.SiO2, CaO.Al2O3.2SiO2, and 2CaO.Al2O3.SiO2

are around 20-30% at 1500 °C and approximately doubled at 1650 °C
• Similar solubilities expected in other complex commercial slags
• Solubility of CaS in blast furnace slag is about 9%

 In practice, however, S concentrations up to about 10% are found and

henrian behaviour is always assumed.

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 Oxidation of Sulphur in the Furnace

 Reaction involving transfer of S from metal to slag

(molecular equation, considering only
[FeS] + (CaO) = (CaS) + [FeO]
CaO and CaS as the slag species)

or, [S] + (O2-) = (S2-) + [O] (more general ionic form)

𝑎𝐶𝑎𝑆 𝑎𝐹𝑒𝑂 𝑎𝑆2− 𝑎𝑂 𝑆 𝑂

𝐾= ≅ ≈
𝑎𝐹𝑒𝑆 𝑎𝐶𝑎𝑂 ℎ𝑆 𝑎𝑂2− 𝑓𝑆 𝑆 𝑎𝑂2−

 Partition coefficient of sulphur or index of desulphurization

(𝑆) 𝑎𝑂2−
= 𝐾 𝑓𝑆
𝑆 𝑂

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 The partitioning of sulphur between slag and metal in laboratory experiments

and in basic steelmaking practice can be described as
log 𝐾1873 = −1.4 𝑁𝐶𝑎 − 1.9 𝑁𝐹𝑒 − 2.0 𝑁𝑀𝑛 − 3.5 𝑁𝑀𝑔 + 1.6 𝑁𝑁𝑎
where NCa etc. are the electrically equivalent ionic fractions

 The approximate dephosphorization power for some basic cations in slag :

Na Ca Fe Mn Mg
1070 : 1.0 : 0.325 : 0.25 : 0.0075

• Na2O is the most powerful, but soda ash cannot be used in steelmaking
because of its tendency to attack and corrode the refractory lining of the furnace.
• FeO as a basic oxide may be used, but it will increase oxygen potential and
hinder S removal
• Most common desulphurizers are CaO and MgO
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 Oxidation of Sulphur in the Ladle

• Carried out using synthetic slag with a high activity of CaO

• Al2O3 and CaF2 are added to reduce the melting point

• An essential point is that it contains no FeO

• Desulphurization by synthetic slags gives satisfactory results

provided that all slags at the end of melting (containing high FeO)
must be removed

• A lid cover prevents metal oxidation and lower FeO content in the bath

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• To increase slag-metal contact surface, liquid metal is poured from

a large height into the ladle with molten synthetic slag.

• Blowing inert gas also induces bath agitation.

• If a synthetic cannot be used, a mixture of solid lime CaO and

fluorspar CaF2 can be used in the ladle before tapping.
Too large addition can lower liquid temperature.

• Addition of deoxidiser to metal decreases [O] and aFeO in liquid

and aids S removal.

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 Conditions for Desulphurization
 Conditions for S removal from the liquid metal

• High K of the equation

(𝑆) 𝑎𝑂2−
 Favoured by high temperature = 𝐾 𝑓𝑆
𝑆 𝑂
• High activity coefficient (i.e., fs) of S in metal
 C, Si and P increases fs
 hot liquid iron is better for S removal than molten steel

• High activity of CaO (i.e., 𝒂𝑶𝟐− ) in slag

 which means highly basic slag.

• Low activity of FeO (i.e., [O]) in metal

 Reaction shows removal of S from hot metal is accompanied by oxygen transfer to metal.
 This oxygen must be removed for efficient desulphurization.

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Effect of slag composition

• In acid slag, 𝒂𝑶𝟐− = 𝟎, thus (S)/[S] is zero.

• Increasing slag basicity (CaO/SiO2), increases (S)/[S]

• Lowering oxygen content (FeO) increases (S)/[S]

In open hearth and oxygen converter

• since steelmaking is carried out in oxidizing conditions (except EAF reducing
slag period), low aFeO is not possible, and thus, the efficiency of desulphurization
is very low.
• The value of index ranges from 50-100 under blast furnace conditions and drops
to 5-10 under basic steelmaking conditions

Efficient stirring
• the liquid bath helps S removal by improving metal-slag contact surface
since S removal takes place at the metal-slag interface
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 B = (%CaO+%MgO)/(%SiO2+Al2O3)

Sulphur distribution between slag and

metal depending on slag basicity at
various activities of ferrous oxide in slag
The influence of basicity and of iron oxide content of the slag on
the distribution of sulphur between slag and metal at 1600°C.
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Principal conditions for efficient desulphurization

1. High activity of CaO in slag

2. Low activity of FeO in slag
3. Low activity of oxygen in metal (metal must be deoxidised thoroughly)
4. Low activity of sulphur in slag
5. High temperature
6. Large contact surface between metal and desulphurizing slag

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 In practice, these conditions are provided by
the following techniques :

1. Addition of lime (CaO) or limestone (CaCO3)

2. Addition of substance to lower slag viscosity

(e.g., Al2O3, CaF2, MnO, etc.)

3. Renewal of slag
(removal of last slag and formation of new slag free from S and FeO)

4. Carried out desulphurization during heat when the metal has the
highest temperature.
At high temperature [C] + (FeO) = {CO} + [Fe] takes place vigorously;
(FeO) is reduced, aCaO increased (by more CaO dissolution), diffusion process
increased, and metal-slag contact surface increased
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5. Treatment in ladle of metal with liquid or solid synthetic slag

containing high aCaO and low aFeO

6. Use of rare-earth elements (Ce, La, etc.) for desulphurization

7. When making steel very low in sulphur

(a) low S charge is selected,
(b) highly basic slag (CaO and CaF2) is blown into the metal
in a jet of inert gas,
(c) CaC2 and other alloys containing Ca or even pure Ca (and also Mg)
are introduced

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